Cationic surface-active agents

ABSTRACT

Cationic surface-active agents which are polyhydroxylated tertiary amines or the quaternary ammonium salts thereof and which are usefully employed in cosmetic compositions, are prepared by condensing on a fatty alcohol, glycerol epihalohydrin alone or together with an epoxide to form polyhalogenated polyethers, which in turn are converted to polyhalogenated glycidyl ethers, the latter being reacted with a secondary amine to form polyhalogenated tertiary amines which are then reacted with sodium or potassium acetate in the presence of a diol to form said polyhydroxylated tertiary amines.

This application is a division of application Ser. No. 891,455, filedMar. 29, 1978, now U.S. Pat. No. 4,220,602, which is a division ofapplication Ser. No. 742,671, filed Nov. 17, 1976, now U.S. Pat. No.4,096,332, which is a division of application Ser. No. 547,465, filedFeb. 6, 1975, now U.S. Pat. No. 4,009,255, which is a division of Ser.No. 187,151, filed Oct. 6, 1971, now U.S. Pat. No. 3,879,464, which is acontinuation-in-part of Ser. No. 655,336, filed July 24, 1967, nowabandoned.

The present invention relates to cationic surface active agents whichare the condensation products of an alcohol having the formula ROH with(a) glycerol epihalohydrin or (b) an epoxide and glycerol epihalohydrin.

I. Surface Active Agents Which Are The Condensation Product Of AnAlcohol And Glycerol Epihalohydrin

In accordance with this embodiment of the present invention there isprovided cationic surface active agents selected from the groupconsisting of

(1) agents having the formula ##STR1## which are hydroxylatedcondensation products of an alcohol having the formula ROH and glycerolepihalohydrin wherein R is a hydrophilic group selected from the classconsisting of linear or branched alkyl and alkenyl having 8-22 carbonatoms, and alkylphenyl having 8-22 carbon atoms, R₁ and R₂ eachindependently are selected from the group consisting of lower alkylhaving 1-4 carbon atoms and hydroxy lower alkyl having 1-4 carbon atomsor together with the nitrogen atom to which they are attached form aring selected from the group consisting of morpholine and piperidine andn is 0.5-10; and

(2) agents which are the quaternary ammonium salts of (1) having theformula ##STR2## where n, R, R₁ and R₂ have the meaning given above, R₃is selected from the group consisting of methyl and ethyl, and Y is ananion selected from the group consisting of Cl, Br, I, SO₄ CH₃, SO₄ C₂H₅, CH₃ SO₃ and ##STR3##

The cationic surface active agents of this embodiment of the inventionare prepared by

(a) condensing on a fatty alcohol or on an alkyl phenol having theformula ROH wherein R has the meaning given above (n+1) moles ofglycerol epihalohydrin having the formula ##STR4## wherein n has themeaning given above and X is halogen, preferably chlorine or bromine toform a mixture of polyhalogenated polyethers having the formula

    RO--C.sub.2 H.sub.3 (CH.sub.2 X)O].sub.n CH.sub.2 --CHOH--CH.sub.2 X (III);

(b) dehydrohalogenating said polyhalogenated polyethers from step (a)with an alkali metal hydroxide or an alkaline earth metal hydroxide toform a mixture of polyhalogenated glycidyl ethers having the formula##STR5##

(c) reacting the polyhalogenated glycidyl ethers from step (b) with asecondary amine to form a mixture of polyhalogenated tertiary amineshaving the formula ##STR6##

(d) replacing the halogen by a hydroxyl in the polyhalogenated tertiaryamines from step (c) to form a mixture of polyhydroxylated tertiaryamines having formula (I) given above.

The various steps in the above process for preparing the surface activeagents represented by formula (I) are as follows: ##STR7##

The quaternization of the surface active agents represented by formula Iyields quaternary ammonium salts having the formula ##STR8## wherein R,R₁, R₂, R₃, Y⁻ and n have the meaning given above.

In the course of the condensation reaction (a) above, when the epoxyring is opened during the polycondensation, a mixture of compoundscomprising the structures ##STR9## is obtained.

Thus a mixture of compounds having the general structure --C₂ H₃ (CH₂X)O-- is obtained. Consequently, the hydroxylated compound of formula Iand II given above represents the two isomers ##STR10## and thecorresponding two isomers of the quaternary ammonium salts.

In the above formulae n is defined by the equation: ##EQU1## wherein Mis equal to the molecular weight of the alcohol or alkyl phenol ROH, Eis equal to the molecular weight of the glycerol epihalohydrin and I isthe hydroxyl index of the condensation product, i.e., the mixture ofpolyhalogenated polyethers repesented by formula (III) above, after step(a).

During the condensation reaction (a) in which (n+1) moles of glycerolepihalohydrin are reacted on one mole of alcohol or alkyl phenol, thenumber of moles of glycerol epihalohydrin fixed by one mole of alcoholor alkyl phenyl to form the recurring units, --C₂ H₃ (CH₂ X)O--, can begreater or smaller than the value of n and a mixture of compounds, allresponding to the general formula III are formed, but in which thenumber of recurring units varies and all those different numbers aredistributed statistically around a mean value represented by n.Consequently, n in the final product represents the mean value or theaverage statistical value of the number of recurring units, --C₂ H₃ (CH₂OH)O--, fixed on the different compounds having the general formula I orII.

An important fact which should be emphasized and which constitutes oneof the essential advantages of the process of preparing thesurface-active agents of this invention is that the present processresults in the formation of compounds having a single lipophilic chainper hydrophilic chain.

Moreover, the process of the present invention permits the regulation ofthe hydrophilic and lipophilic properties of the final product. Thehydrophilic characteristic of the resulting surface active agents can beregulated by choosing the value of the number n of moles of glycerolepihalohydrin to be reacted with one mole of fatty alcohol or alkylphenol. The lipophilic characteristic of the resulting surface activeagents can be regulated by choosing the length of the hydrocarbon chainR in the fatty alcohol or alkyl phenol used as an initial reactant.

The following is a detailed description of a preferred embodiment ofproducing the above surface-active agents.

In step (a), the condensation of glycerol epichlorohydrin or glycerolepibromohydrin on the fatty alcohol or alkyl phenol is carried out inthe presence of an acid catalyst, such as boron trifluoride, stannicchloride or antimony pentachloride, at a temperature between 25°-160° C.Preferably boron trifluoride is employed at a temperature between60°-120° C. The proportion of BF₃ with respect to the total mass ofreactants ranges between 0.1-0.2 weight percent.

In step (b), the polyhalogenated polyethers, represented by formula(III) above, which result from step (a), are converted to glycidylethers (Formula IV) by dehydrohalogenation of the halohydrin, using anaqueous solution of an alkali or alkaline earth metal hydroxide, havinga concentration, by weight, of from 20-50 percent. The molar ratio ofalkali or alkaline earth metal hydroxide to polyhalogenated polyetherranges between 1:1 to 1:2 and preferably between 1:1.2 to 1:1.5. Duringthis phase of the overall process, which ordinarily is initiallyconducted at about 20° C. or ambient temperature, the reactiontemperature rises to about 100° C. When the exothermicity of thereaction ceases, the reaction is terminated by heating the reactionmixture in a water bath. This dehydrohalogenation operation is generallyconducted in the presence of a solvent to obtain high reaction speedsand high epoxidation yields. The solvent employed should, preferably,not be miscible with concentrated aqueous solutions of electrolytes sothat the resulting polyhalogenated glycidyl ethers can be separated fromthe reaction medium simply by decantation. Tertiary butyl alcohol and2-butoxy ethanol are particularly useful solvents when used in weightproportions essentially equal to that of the halohydrin to bedehydrohalogenated. Quaternary ammonium salts comprising a lipophilicchain can be used to improve the contact between the reactants. Theresulting polyhalogenated glycidyl ether, if desired, can be isolated byevaporation of the solvent or it can be used in solution in thesubsequent stage, i.e., step (c).

In step (c), the polyhalogenated glycidyl ethers from step (b) arereacted with a secondary amine at a temperature from 25°-120° C. to openthe epoxide ring and thereby form the polyhalogenated tertiary amineshaving formula (IV).

Alternatively, the polyhalogenated tertiary amines of formula (IV) canbe prepared in a single step by reacting the polyhalogenated polyethersfrom step (a) with a secondary amine in the presence of an alkali oralkaline earth metal hydroxide.

Representative secondary amines usefully employed in the presentinvention include diethylamine, dipropylamine, morpholine, piperidineand alkanolamines such as diethanolamine, diisopropanolamine,diglycerylamine and N-ethylethanolamine.

The molar ratio of secondary amine to polyhalogenated glycidyl ether instep (c) or the ratio of secondary amine to polyhalogenated polyether(when the alternate route is practiced) to produce polyhalogenatedtertiary amines is between about 1:1 to 1:1.5 and, preferably, about1:1.2.

In step (d), the replacement of the halogen by a hydroxyl in thepolyhalogenated tertiary amine from step (c), or from its alternateroute, yields the polyhydroxylated amines of the present invention whichare useful surface active agents and which are represented by formula I.This operation is carried out with an alkaline salt of a carboxylicacid, such as sodium or potassium acetate, at a temperature between150°-200° C., preferably about 180° C., in the presence or absence of asolvent.

The presence of a solvent in the reaction medium during step (d) assuresboth instantaneous and progressive contact among the reactants and easyseparation therefrom of the mineral halide formed. Suitable solventsinclude ethylene glycol, diethylene glycol, propylene glycol,dipropylene glycol as well as the monoalkylethers of these diols suchas, monobutyl ether of ethylene glycol and monobutyl ether of diethyleneglycol. The hydroxylated solvents also intervene by alcoholysis of theesters formed in an intermediate step.

When the reaction is carried out in the absence of a solvent, as may bethe case when the alkaline salt of carboxylic acid is somewhat solublein the reaction medium, the polyhydroxylated tertiary amine is obtainedby alcoholysis of the esters of carboxylic acid with a lower alcoholsuch as methanol or ethanol, or by saponification followed by saltingout or extraction.

In one preferred commercial exploitation of the present invention, thepolyhalogenated polyethers from step (a) are reacted with a secondaryamine, as defined above, in the presence of an alkali or alkaline earthmetal hydrooxide, without isolating the glycidyl ethers thus formed.After reaction with an alkaline salt of carboxylic acid, the esterifiedamino ethers are separated from the mineral halide by filtration orwashing, and then the salts of carboxylic acid are regenerated in situfrom the carboxylic esters by saponification with an alkaline hydroxide.Thus, the alkaline salt of carboxylic acid is recovered in aqueoussolution and can be used for another hydroxylation reaction.

As stated above, the surface-active agents of this embodiment of thepresent invention also include the quaternary ammonium salts of thecompounds represented by formula I, the quaternary ammonium salts beingrepresented by formula II. To produce said quaternary ammonium salts,the compounds represented by formula I can be reacted with, for instancea quaternizing agent such as methyl sulfate, ethyl sulfate, ethylchloride, ethyl bromide, methyl iodide, methyl paratoluylene sulfate ormethyl methane sulfonate. The mole ratio of quaternizing agent to thecompounds represented by formula I corresponds to the stoichiometricamount or is slightly inferior and the reaction is carried out at atemperature ranging from about 15° to 100° C. at atmospheric pressure.

Compared, for example, with fatty amines, the surface active agents ofthe present invention are significantly more water soluble especially atabout neutral pH and they lack the odor characteristic of fatty amineand derivatives thereof.

Additionally, the process of the present invention yields stablesurface-active agents which are soluble in water over a very wide pHrange. The present process also provides surface-active agents which aresoluble in concentrated sodium hydroxide without risk of instabilitywhich occurs, for example, with the quaternary ammonium hydroxides.Moreover, this result is obtained without the introduction ofsupplementary ionic groups, and especially anionic groups, which impairthe substantive characteristics of the surface-active agents. Thesolubility characteristics of the surface-active agents of thisinvention are, of course, highly variable as a function of the values ofn, R, R₁, and R₂. Certain of these agents in which R represents alkyl oralkaryl and in which n is equal to 5-6 are soluble in sodium hydroxide.The extent to which these surface-active agents may irritate the skinand mucous membranes is also dependent on the values of n, R, R₁ and R₂.In general, however, the surface-active agents of this invention areclearly less irritating than fatty amines and their derivatives.

The surface active agents of the present invention also provideadvantages not secured by such prior art compounds as those disclosed inLuxembourg application No. 48,458 filed Apr. 23, 1965 which arenon-ionic surface-active agents having the formula

    RO--C.sub.2 H.sub.3 (CH.sub.2 OH)O].sub.n H

In contradistinction, the surface-active agents of the present inventioncontain a hydroxy amino propane group ##STR11## which imparts theretotheir cationic characteristics and their substantivity, i.e., theiraffinity for fibers and particularly for animal and vegetable fibers.

The surface-active agents of the present invention also comparefavorably with amino polyethers having the formula ##STR12## and thesubstitution of a --C₂ H₃ (CH₂ OH)O-- group for the oxyethylene group--OCH₂ CH₂ -- is very useful.

The surface-active agents of this embodiment of the present inventionbecause of their physical and chemical characteristics are suitablyemployed in cosmetic preparations, and particularly in shampoo, hairdyes hair rinses and permanent waving compositions. Further when thesurface-active agents of this embodiment of the present invention areused in compositions for treating hair, they impart to the hair acertain sheen and a pleasing texture. The hair is particularly soft,odorless and is easily untangled.

Thus, in accordance with the present invention there is provided ashampoo composition comprising an aqueous solution of the surface-activeagents of this invention present in amounts of about 0.5 to 10 percentby weight of said shampoo composition, having a pH ranging from about 3to 6.5. The pH can be adjusted to the desired value by incorporatinginto said composition an acidic component such as an organic acidincluding lactic, acetic or citric acid and the like.

In another embodiment of the present invention hair is permanently wavedby applying to the hair wound on curlers during the first stage, i.e.,during the reducing stage, a composition comprising reducing agent,permitting the composition to remain on the hair for a time sufficientto alter the disulphide bonds of the keratin of the hair, generallyabout 10-40 minutes, thoroughly rinsing the hair to remove residualreducing agent and applying in the second stage, i.e., during theneutralization stage, a cosmetic composition comprising a mixture of anoxidizing or neutralizing agent and the surface-active agent of thepresent invention, whereby the disulphide bonds of the keratin of thehair are reformed.

Conventional reducing agents employed are advantageously those organicthiols which are generally used to perform the first stage of apermanent waving operation. Representative thiols include thioglycolicacid and its salts, glycol thioglycolate, glycerol thioglycolate,thioglycolic amide, thiolactic acid, glycol thiolactate,β-mercaptoethanol, N-carboxymethyl mercapto acetamid, β-mercaptopropionic acid and the like. Generally the composition comprising thereducing agent is an aqueous solution of said reducing agent present inamounts of about 2 to 15 percent by weight thereof and having a pHranging from about 8 to 10.

The neutralizing composition of the present invention comprises anaqueous solution of 0.5 to 4 weight percent of a conventionalneutralizing or oxidizing agent and about 0.2 to 5 weight percent of thesurface active agent of this invention. Conventional neutralizing agentsemployed include, for instance, hydrogen peroxide, sodium or potassiumbromate, sodium perborate or percarbonate and the like.

The surface-active agents of the present invention are also usefullyemployed in hair dye compositions comprising a solution in a solventselected from the group consisting of water, an aqueous solution of alower alkanol such as ethanol and isopropanol, of a glycol such as butylglycol, propylene glycol, ethylene glycol, 3-amyloxy 4-propane 1,2-diol,and of ethers of glycol such as monobutyl ether of ethylene glycolwherein said alkanol and/or glycol and/or ether of glycol is present inamounts of about 8 to 25 percent by weight of said solution, a hair dyesuch as azo, anthraquinone and nitro dyes of the benzene series, and 0.5to 6 percent by weight of the surface-active agent of the presentinvention.

Additionally, if desired, said hair dye composition can include itsweight of 6% hydrogen peroxide to provide said composition in gel form.

Generally the dye is present in amounts of about 0.1 to 5 percent byweight of said composition which has a pH ranging from about 8 to 10.5.

Representative dyes include paraphenylene diamine, 2,5-toluene diaminesulfate, chloroparaphenylene diamine sulfate, nitroparaphenylenediamine, 1,2,4-triaminobenzene trihydrochloride, paraaminodiphenylamine, ortho phenylene diamine, 4-chloro ortho phenylene diamine,4-nitro ortho phenylene diamine, paraaminophenol, 4-amino 2-methylphenol sulfate, 4-amino-3-methyl phenol, 4-amino 2-nitro phenol,m-diamino anisol and its sulfate, p-aminophenol and its sulfate,nitro-p-phenylene diamine, p-toluylene diamine, resorcine, hydroquinone,3-nitro 4-β-aminoethylamino anisole hydrochloride, 2-4-diaminophenolhydrochloride, paramethyl aminophenol sulfate, ortho aminophenol,4-chloro 2-aminophenol, 4-nitro 2-aminophenol, 5-nitro 2-aminophenol,4,6-dinitro 2-aminophenol, 6-chloro 4-nitro 2-aminophenol hydrochloride,4-amino diphenylamine, 4,4'-diamino diphenylamine sulfate, metaphenylenediamine, chloro-meta phenylene diamine, nitro-meta phenylene diamine,meta toluylene diamine, 2,4-diamino anisol sulfate, meta aminophenol,3,5-diaminophenol hydrochloride, diethyl meta aminophenol, paraaminoortho cresol, 1-dimethylamino 3-amino ethylamino 4-nitro benzene,1-hydroxy-2,4-di(p-trimethylammoniumphenylamino) anthraquinonemethosulfate, 1-hydroxy-2,4-di (p-trimethyl-ammoniumphenylamino)anthraquinone iodide, 1-amino propylamino anthraquinone, 1,8-Bis-γ-aminopropylamino anthraquinone, 1-diethylamino2-ethylamino-nitro-4-NN-dihydroxyethylamino benzene dihydrochloride,4-N-methylamino-3-nitro-1-N-β-aminoethylamino benzene, [I-hydroxy-4-(γmethylmorpholinium) propylamino anthraquinone]methyl sulfate,2-β-aminoethylaminoanthraquinone, 1,5-di-(β-aminopropylamino)anthraquinone, 1-methylamino-4-amino propylamino anthraquinone, 1-aminopropylamino-anthraquinone 1,4-diamino-5-γaminopropylamino-anthraquinone. Additional examples of commerciallyavailable useful dyes include, as monoazo dyes, Cl Acid Blue 92 (13390)and CI Acid Yellow 23 (19140); as diazo dyes, Cl Acid Orange 24 (20170);as triphenylmethane type dyes, Cl Acid Blue 1 (42045), Cl Acid Violet 19(42685), Cl Acid Blue 22 (42755) and Cl Acid Violet 15 (43525); asxanthene dyes, CI Acid Violet 9 (45190); as azine dyes, Cl Acid Black 2(50420), Cl Acid Blue 59 (50315) and Cl Acid Blue 61 (50330); asanthraquinone dyes, Cl Acid Violet 43(60730), Cl Acid Blue 80 (61585),Cl Acid Violet 51 (62165) and Cl Acid Blue 138 (62075); as premetallizeddyes, both 1:1 and 2:1 complexes, chromium and cobalt, for instance ClDisperse Blue 14 (61500), Cl Disperse Blue 6 (62050) and Cl DisperseBlue 31 (64505); as direct dyes, Cl Direct Blue 2 (22590), Cl DirectBlack 51 (27720) and Cl Direct Violet 51 (27905); and as solvent dyes,(15680) and Cl Solvent Violet 10 (45190).

The surface-active agents of the present invention are also usefullyused in hair rinses. These hair rinses are employed on the hair in orderto make easier its disentanglement, especially when same is electric orcurly.

These hair rinses comprise a solution in a solvent selected from thegroup consisting of water and an aqueous solution of a lower alkanolsuch as ethanol and isopropanol wherein said alkanol is present inamounts of about 15 to 60% by weight of said solution, a cosmetic resinin amounts of about 0.5 to 5% and 0.1 to 2% by weight of surface-activeagents of the present invention. This composition may also comprise aperfume in amounts of about 0.05 to 0.5% and hair dyes from an amount ofabout 0.005 to 3% said composition which has a pH from about 7 to 8.5.Representative cosmetic resins include polymers, i.e. polyvinylpyrrolidone (PVP) having a molecular weight ranging between 40,000 to360,000 the preferred molecular weight being 40,000, or copolymers suchas the copolymer of polyvinyl pyrrolidone and vinyl acetate(MW=40,000-160,000) 70%:30% to 30%:70%, the preferred proportion being60%:40% having a viscosity of 3,3 to 4 centipoises in 5% solution inethanol; or copolymers of crotonic acid and vinyl acetate 90%:10% havinga molecular weight of 40,000 to 200,000 and preferably of 50,000 and aviscosity of 7 to 9 centipoises in 5% solution in tetrachlorethane; ormonoalkyl ester of the copolymer of methylvinyl ether and maleic acid.

Representative hair dyes include direct dyes such as azo dyes,triphenylmethane type dyes, xanthene dyes, anthraquinone dyes, azinedyes, premetallized dyes, solvent dyes and the like. All the above citeddyes as commercially available useful dyes may be used.

In use, the compounds of the present invention can be in the form ofsalts of inorganic and organic acids such as hydrochloric, phosphoric,boric, acetic, citric and lactic acids.

II. Preparation of Surface-Active Agents Which Are The CondensationProduct Of An Alcohol And Glycerol Epihalohydrin Example 1

185 g of glycerol epichlorhydrin are reacted with one mole, i.e., 186 gof dodecanol at 75°-80° C. in the presence of 1.5 ml of an acetic acidcomplex containing 36% BF₃. Dodecyl ether of polyepichlorohydrin havingthe following formula is obtained:

    C.sub.12 H.sub.25 O--C.sub.2 H.sub.3 (CH.sub.2 Cl)O].sub.n CH.sub.2 CHOH--CH.sub.2 Cl

in which n has a statistical average value of 1.

371 g of this compound are dissolved in an equal weight of tertiarybutyl alcohol and 148 g of an aqueous 40% solution of sodium hydroxideare added drop by drop, while stirring.

The temperature rises from 25° to 28° C.

The mixture is then heated to 65°-70° C. while stirring.

After being cooled to ambient temperature, the sodium chlorideprecipitate is dissolved by adding 300 cm³ of water.

The aqueous phase containing the sodium chloride and the excess sodiumhydroxide is drawn off.

The organic phase is left overnight, then filtered.

After evaporation of the tertiary butyl alcohol first under normalpressure, then under the vacuum of a water-jet pump, the glycidyl etherhaving the following formula is collected: ##STR13## with a 98% yield.

The resultant product has an epoxide content equal to 97% of thetheoretical value.

160.5 g are added to 69 g of 97% pure diisopropanolamine.

The mixture is heated to 95° C. for 31/2 hours and the tertiary aminehaving the following formula is obtained with a 94% yield: ##STR14## Inthis formula n has a statistical average value of 1. This compound iswater soluble in an acid medium.

222 g of this chlorinated amine are then heated with 46.6 g of potassiumacetate in the presence of 260 g of dipropylene glycol at 180°-185° C.for 3 hours.

The potassium chloride is separated by filtration, then the dipropyleneglycol is evaporated in a vacuum.

In order to complete the de-acetylation, 166 g of the product aredissolved in 200 g of absolute ethyl alcohol. 1 cm³ of a 25% solution ofsodium methylate in methanol is added and the mixture is left at ambienttemperature for 18 hours.

The ethyl acetate formed and the alcohol, are evaporated, and 163.5 g ofthe compound having the following formula are collected: ##STR15## Heren has a statistical average value of 1.

This product is in the form of a colorless viscous oil, soluble inwater, with a pH less than or equal to 7, this pH being adjusted byadding lactic acid.

Example 2

The process is the same as in Example 1, except that thediisopropanolamine is replaced by diethanolamine. The polychlorinatedtertiary amine having the following formula is prepared: ##STR16## nhaving a statistical average value of 1 with a yield of about 93%.

After treatment with potassium acetate at 180°-185° C. in dipropyleneglycol, filtration, evaporation of the dipropylene glycol andethanolysis, the compound having the following formula is obtained:##STR17## n has a statistical average value of 1.

This compound takes the form of a viscous yellow oil, soluble in waterand having a pH less than or equal to 7.5. It forms gels at a 4%concentration at a pH of 7.5 to 7.2 in an aqueous medium (the pH beingadjusted with lactic acid).

Example 3

4.5 moles of glycerol epichlorohydrin are reacted with 3 moles of amixture of fatty alcohols containing about 55% dodecanol and 43.5%tetradecanol. The product is monoalkyl ether of polyepichlorohydrinhaving the formula:

    RO--C.sub.2 H.sub.3 O(CH.sub.2 Cl)].sub.n CH.sub.2 --CHOH--CH.sub.2 Cl

in which n has a statistical average value of 0.5 and R represents analkyl radical with 12 to 14 carbon atoms.

This compound is then dehydrohalogenated according to the processdescribed in Example 1.

Glycidyl ether having the following formula is obtained: ##STR18## inwhich R and n have the meaning given above.

On being heated at 90°-95° C. for 2 hours, this product reacts with thediisopropanolamine at a 5% molar excess to form the tertiary amine:##STR19## with a 94% yield.

Then, after treatment with potassium acetate at 180°-185° C.,dipropylene glycol being used as the solvent, filtration of thepotassium chloride and evaporation of the solvent, the polyhydroxylamine having the following formula is obtained: ##STR20## with n and Rhaving the meaning given above.

Example 4

The process is the same as in Example 3, except that thediisopropanolamine is replaced by diethanolamine in identical molarproportions. The chlorinated amine having the following formula isprepared: ##STR21## R is alkyl having 12-14 carbon atoms, n has astatistical average value of 0.5.

By hydroxylation at 180°-185° C. for 3 hours in dipropylene glycol, witha stoichiometric quantity of potassium acetate with respect to thechlorine, the polyhydroxyl amine having the following formula isobtained: ##STR22## in this formula R and n have the meaning givenabove.

Example 5

By condensation of 2 moles of glycerol epichlorohydrin on one mole of amixture of fatty alcohols identical to that used in Examples 3 and 4,the monoether of polyepichlorohydrin having the following formula isfirst prepared:

    RO--C.sub.2 H.sub.3 (CH.sub.2 Cl)O].sub.n CH.sub.2 --CHOH--CH.sub.2 Cl

in which R represents an alkyl having 12 to 14 carbon atoms and n has astatistical average value of 1.

This product is then dissolved in tertiary butyl alcohol anddehydrohalogenated with an aqueous 40% solution of sodium hydroxide inan excess of 50% with respect to the quantity theoretically necessary.

After decantation of the organic phase, drying on sodium sulfate, andevaporation of the tertiary butyl alcohol, glycidyl ether having thefollowing formula is obtained: ##STR23## In this formula R and n havethe same meaning as above.

Yield: 98.5%.

Epoxide content: 100% of the theoretical value.

This product, when reacted at 95° C. with diethanolamine in a molarexcess of 5% yields the chlorinated amine having the following formula:##STR24## again R and n have the meaning given above.

Yield: 98%.

Potassium acetate at a molar excess of 10% is then substituted for thechlorine at 180°-185° C., using a quantity of dipropylene glycol equalin weight to that of the chlorinated amine as the solvent.

The potassium chloride is removed by filtration and the solvent isevaporated in a vacuum.

The raw product, in which about 7% of the alcohol functions areesterified by acetic acid, is purified in the following manner:

The esters are saponified with an aqueous 14% solution of sodiumhydroxide in stoichiometric proportions.

The hydroxyl amine is dissolved in an equivalent weight of butylmonoether of diethylene glycol. The organic phase is washed twice withboiling water, and the liquid is decanted while hot.

After removal of the water and solvent, a compound having the followingformula is obtained: ##STR25## wherein R and n have the meaning givenabove.

This product is a yellow-orange oil which is soluble in water at a pH of7 (the pH being adjusted by the addition of lactic acid).

Example 6

By using the same glycidyl ether as in Example 5, but replacing thediethanolamine with morpholine in the same molar proportions, thechlorinated amine having the following formula is obtained: ##STR26## inthis formula R represents an alkyl radical with 12 to 14 carbon atomsand n has a statistical average value of 1.

This product is then dissolved in an equivalent weight of monobutyletherof diethylene glycol and heated to 180°-185° C. for 4 hours with a 10%excess of potassium acetate.

After the potassium chloride has been separated by filtration, theacetic esters are saponified with aqueous soda in a stoichiometricquantity. A weight of water equal to that of the filtrate is added andthe mixture is heated to 70° C. It separates into two phases.

The aqueous phase, containing the sodium acetate, is drawn off whilehot.

The water and solvent are evaporated together from the organic phase byprogressive elevation of the temperature to 180° C. under a pressure of18 mm of mercury.

An orange oil is obtained.

This product has the following formula: ##STR27## in which R representsalkyl having 12 to 14 carbon atoms and n has a statistical average valueof 1. The product is soluble in water which has been acidified withlactic acid to pH 6.3.

Example 7

2 moles of epichlorohydrin are reacted with one mole of industrial oleylalcohol. The monoether of polyepichlorohydrin having the followingformula is obtained:

    RO--C.sub.2 H.sub.3 (CH.sub.2 Cl)O].sub.n CH.sub.2 --CHOH--CH.sub.2 Cl

In this formula R represents the 9-octadecenyl radical, n having astatistical average value of 1.

After treatment with an aqueous solution containing 40% sodium hydroxideat an excess of 50% in the presence of tertiary butyl alcohol, thisyields the corresponding glycidyl ether.

Yield: 98%.

Expoxide content: 98% of the theoretical value.

The tertiary chlorinated amine having the following formula ##STR28##with R and n having the meaning given above, is prepared by heating thisepoxide with diethanolamine at a 5% molar excess, the temperature beingheld at 95° C. for 2 hours.

Hydroxylation is then carried out as described above, with potassiumacetate and dipropylene glycol.

After filtration of the salt and evaporation of the solvent, theresultant product may be purified as follows:

200 g of the product are dissolved in 200 g of monobutylether ofdiethylene glycol.

The acidic esters are saponified by addition of a stoichiometricquantity of an aqueous solution containing 40% sodium hydroxide. Then200 g of hot water are added, the mixture is stirred for severalminutes, and the aqueous phase containing the sodium acetate is drawnoff.

After evaporation of the water and solvent, 195 g of the product havingthe following formula are collected: ##STR29##

This compound is soluble in water at a pH of about 6.5, this pH beingadjusted with lactic acid.

Example 8

From the oleyl alcohol identical to that used in Example 7, thefollowing compounds are successively prepared. First, the oleyl ether ofpolyepichlorohydrin having the formula:

    RO--C.sub.2 H.sub.3 (CH.sub.2 Cl)O].sub.n CH.sub.2 --CHOH--CH.sub.2 --Cl

in which:

R=9-octadecenyl(oleyl), and

n has a statistical average value of 3, and then the correspondingglycidyl ether having the formula: ##STR30## wherein R and n have themeaning given above.

By opening the epoxide with diethanolamine under the same conditions asbefore, the following chlorinated amine is obtained: ##STR31## wherein Rand n have the meaning given above.

This product is then dissolved in an equivalent weight of monobutyletherof diethylene glycol and heated to 180°-185° C. for 3 hours withpotassium acetate.

1.10 mols of potassium acetate are used per gram-atom of chlorine.

The percent transformed, calculated on the basis of the consumption ofthe acetate, is about 98%.

The potassium chloride is separated by filtration. The solvent is thenevaporated in a vacuum by progressively raising the temperature to 180°C.

The raw product is dissolved in alcohol, decolorized with animalcharcoal, then ethanolyzed with sodium methylate as a catalyst.

0.5 g of catalyst are used per 100 g of the product.

The alcohol and ethyl acetate which has formed are evaporated.

The polyhydroxylated amine having the following formula is obtained:##STR32## R=9-octadecenyl and n has a statistical average value of 3.

This is a very viscous oil which is soluble in water at 25° C. The pH ofa M/10 solution is about 9.3.

Example 9

After reacting 264 g of "Hexadecylic" alcohol (sold commercially theEsso Corporation) with 185 g of epichlorohydrin at 60° C. in thepresence of 1.2 ml of an acetic acid complex of boron fluoride, apolychlorinated polyether having the following formula is obtained:##STR33## n has a statistical average value of 1.

In 200 g of monobutylether of diethylene glycol at ambient temperature,the following are successively dissolved:

179.6 g of polychlorinated polyether and

46 g of diethanolamine at 96%.

Then, drop by drop, 44 g of an aqueous 40% solution of sodium hydroxideare added. The temperature of the reaction mixture rises to 32°.

The mixture is stirred for 15 minutes first, at ambient temperature andthen in a boiling water-bath for one hour.

A polychlorinated amine having the following formula is thus obtained:##STR34## wherein n has a statistical average value of 1.

This product is soluble in water in an acid medium.

The hydroxylation reaction is carried out as follows:

The excess sodium hydroxide is neutralized with 2.4 g of pure aceticacid. Then 31.8 g of anhydrous sodium acetate are added.

The mixture is heated to 185°-190° C. for 6 hours after the water hasbeen removed by evaporation.

The sodium chloride is separated by filtration; then the acetic estersformed are separated with 37.6 g of a 40% solution of sodium hydroxide.

After addition of 650 g of water, the mixture is heated to 90° C.

When allowed to settle, the mixture separates into two phases. Theaqueous phase containing the electrolytes is drawn off, then the solventof the organic phase is evaporated.

180 g of the product having the following formula are obtained:##STR35## wherein n has a statistical average value of 1.

This compound is a clear yellow oil and is soluble in water at a pH of3.

The tertiary amines prepared in the preceding Examples may betransformed into quaternary ammonium salts. This may be done veryeasily, particularly by using methyl sulfate, as shown in the followingexample:

Example 10

To 50 g of a polyhydroxylated tertiary amine having the followingformula: ##STR36## wherein R represents an alkyl radical having 12 to 14carbon atoms n has a statistical average value of 0.5, 14.7 g of methylsulfate are added, drop by drop, at 40° C. The temperature of themixture rises to 70° C.

The addition of the methyl sulfate takes about 15 minutes. The reactionis terminated by heating in a boiling water bath.

The product is a water-soluble paste and has the following formula:##STR37## wherein R and n have the meaning given above.

Example 10 is repeated using, instead of methyl sulfate, essentiallycomparable amounts of ethyl chloride, ethyl bromide, methyl iodide,methyl paratoluylene sulfate and methyl methane sulfonate to obtainsimilar quaternary ammonium salts.

Example 11

The monoether of polyepichlorohydrin, having the following formula, isprepared by condensing 2 moles of glycerol epichlorohydrin on a molarequivalent quantity of a mixture of fatty alcohols identical to thatused in Examples 3, 4 and 5:

    RO--C.sub.2 H.sub.3 (CH.sub.2 Cl)O].sub.n CH.sub.2 --CHOH--CH.sub.2 Cl

In this formula:

R represents alkyl having 12 to 14 carbon atoms, and n has a statisticalaverage value of 1.

40.5 g of anhydrous diethylamine are added to 191 g of this product.Then 55.5 g of an aqueous 40% solution of sodium hydroxide are added tothe mixture in 5 minutes with stirring. The temperature rises from 25°to 31° C. The reaction mixture is progressively heated to 90° C. in 35minutes and is kept at this temperature for one hour.

After the electrolytes have been dissolved in 76 g of water, achlorinated amine having the following formula is separated by saltingout at 90° C.: ##STR38## wherein R and n have the meaning given above.

After dehydration the product is 93% pure according to amino groupdeterminations. The chlorine is substituted using potassium acetate indipropylene glycol at 180° C.

This process takes three hours. The raw product collected afterfiltration and evaporation of the solvent is deacetylated bysaponification with sodium hydroxide and washed with an equivalentweight of water at 80°-85° C. After decantation and dehydration in avacuum, a yellow-orange oil having the following formula is obtained.##STR39## wherein R and n have the meaning given above.

This compound is soluble in water at a pH less than or equal to 6 (thepH being adjusted with lactic acid).

Example 12

As in Example 7, a monoether of polyepichlorohydrin having the followingformula is first prepared:

    RO--C.sub.2 H.sub.3 (CH.sub.2 Cl)O].sub.n CH.sub.2 --CHOH--CH.sub.2 Cl

In this formula:

R represents an 9-octadecenyl and

n has a statistical average value of 1.

This product is then condensed with morpholine at 95° C. in the presenceof sodium hydroxide. The process takes 11/2 hours. The molar proportionsof sodium hydroxide to chlorohydrin and amine to chlorohydrin are1.05:1.

After neutralization of the excess sodium hydroxide with acetic acid, achlorinated amine having the following formula is obtained: ##STR40##wherein R and n have the meaning given above. This product is mixed withan equivalent weight of diethylene glycol and reacted with sodiumacetate at 180°-185° C. for 31/2 hours. This reactant is added as anaqueous solution, the water being removed from the reaction medium byevaporation. 1.05 moles of acetate are used per atom of chlorine to bereplaced.

After removal of the salt by filtration and evaporation of the solvent,the product is a brown oil. It is soluble in water at a pH less than orequal to 4.5 (the pH being adjusted with lacetic acid). It has thefollowing formula: ##STR41## wherein R and n have the meaning givenabove.

Example 13

By the same process as in Example 12, except that morpholine is replacedby diisopropanolamine, a compound having the following formula isprepared: ##STR42## In this formula: R represents 9-octadecenyl and

n has a statistical average value of 1.

This product is soluble in water at a pH less than or equal to 5.5 (thepH being adjusted with lactic acid).

Example 14

The procedure is the same as in Example 12, except that instead of usingoleyl alcohol having an 85% purity (as in Examples 7, 12 and 13), thefirst step is to prepare from an oleyl-cetyl alcohol sold under thetrademark "Ocenol HD-50-55" by the Dehydag Company, which is acommercial "oleyl-cetyl" alcohol, having an iodine index of 45-55, achlorinated amine having the formula: ##STR43## wherein R represents ahydrocarbon radical having 12 to 18 carbon atoms, and

n has a statistical average value of 1.

The chlorine is then substituted using potassium acetate in dipropyleneglycol as a solvent.

Reaction temperature: 180°-185° C.

Duration: 51/2 hours.

The product obtained after filtration and evaporation of the solvent hasthe following formula: ##STR44## wherein R and n have the meaning givenabove.

Ocular tests on rabbits have shown it to be absolutely harmless whenapplied as an aqueous solution having a pH of 4 and an active productconcentration of 1/10 mole/liter.

Example 15

The monoether of polyepichlorohydrin having the following formula isprepared by reacting two moles of epichlorohydrin with a molarequivalent quantity of 2-octyldodecanol (sold under the trademark"EUTANOL-G") in the presence of 1.2 ml of an acetic acid complex ofboron fluoride: ##STR45## wherein n has a statistical average value of1.

This compound is then condensed with morpholine in the presence ofsodium hydroxide.

Molar proportion of morpholine:chlorohydrin= 1.05

Molar proportion of sodium hydroxide:chlorohydrin= 1.10

The mixture is heated to 95° C. for 21/2 hours.

A chlorinated amine having the following formula: ##STR46## wherein nhas the meaning given above and obtained after washing and dehydration,has an amine group content of 1.70 meq/g.

The chlorine is then substituted by heating said amine at 180°-185° C.with a 5% excess of anhydrous potassium acetate with respect to thequantity theoretically necessary. Dipropylene glycol is used as thesolvent. The process takes four hours.

After filtration and evaporation of the dipropylene glycol, the aceticesters are saponified with an aqueous 40% solution of sodium hydroxide.Then the product is washed with a mixture of equal weights of water andmethanol.

A polyhydroxylated amine having the following formula: ##STR47## inwhich n has a mean statistical value of 1, is obtained in the form of ayellow-orange oil.

Example 16

The monoether of polyepichlorohydrin, having the following formula, isprepared by reacting 3 moles of glycerol epichlorohydrin with 0.5 moleof nonylphenol in the presence of 0.85 ml of acetic of boron fluoride at70°-85° C.: ##STR48## In this formula n has a statistical average valueof 5. The theoretical hydroxyl index of this product is 72 (found 85).150 g of this polychlorinated polyether are treated with 26.6 g ofdiethanolamine in the presence of 23.9 g of an aqueous 40% solution ofsodium hydroxide. 215 g of diethylene glycol are used as a solvent.After 2 hours of heating at 90°-95° C., the percentage of transformationis about 95%.

A polychlorinated teriary amine having the following formula isobtained: ##STR49##

The chlorine is then replaced as follows:

The sodium hydroxide is remaining in the reaction mixture is neutralizedwith acetic acid. The mixture is heated to 180°-185° C. and 0.5 mole ofaqueous sodium acetate is added in 45 minutes. The water is removed byevaporation. After an hour of heating at 180°-185° C., 45.1 g of anaqueous 40% solution of sodium hydroxide are added in 11/2 hours, andthe sodium acetate is thus recovered from the acetic esters previouslyformed. The temperature is kept at 180°-185° C. for 21/2 hours after thesodium hydroxide has been added. After cooling, the salt is removed byfiltration and the diethylene glycol is evaporated under reducedpressure. A polyhydroxylated amine having the following formula isobtained: ##STR50## In this formula n has a statistical average value of5.

The product is soluble in water at a pH of 9 and in a 10% sodiumhydroxide solution.

Example 17

By proceeding as in Example 16, except that the diethanolamine isreplaced by morpholine, a polyhydroxylated amine having the followingformula is prepared: ##STR51## wherein n has a statistical average valueof 5.

This compound is soluble in water, the pH of the solution being 9.

Examples 16 and 17 are repeated using, instead of nonylphenol,comparable amounts of octylphenol and dodecylphenol.

Example 18

An alcohol having an average molecular weight of 290 is prepared bycatalytic reduction, in the manner conventionally used to reduce fattyalcohols, of the isostearic acid sold commercially by the Emery Company.

The isostearic acid used has the following properties:

Iodine index: 10

Saponification index: 5.6

Titer: 10°

By reacting 0.3 mole of alcohol with 0.6 mole of epichlorohydrin in thepresence of 0.4 ml of an acetic acid complex of boron fluoride at70°-75° C., a polychlorinated polyether having the following formula isobtained:

    RO--C.sub.2 H.sub.3 (CH.sub.2 Cl)O].sub.n CH.sub.2 --CHOH--CH.sub.2 Cl

wherein R represents an alkyl radical derived from isostearic acid, andn has a mean statistical value of 1.

60 g of the clear yellow oil which results in mixed with 19 g ofdiisopropanolamine. Then 14.5 g of an aqueous 40% sodium hydroxidesolution are added.

After 11/2 hours of heating at 95° C., the product is completely solublein water in an acid medium. From a determination of the tertiary amines,the percentage of transformation is approximately 100%.

The resulting chlorinated amine is now changed to a polyhydroxylatedamine as follows:

The following substances are successively added to the reaction mixture:

0.8 ml of glacial acetic acid,

120 g of dipropylene glycol, and

11.45 g of anhydrous potassium acetate.

The mixture is heated to 180°-185° C. for 6 hours. After cooling thesalt is removed by filtration and the dipropylene glycol is evaporatedunder reduced pressure.

The resulting product, whose saponification index is 5.6, is treatedwith 1 g of an aqueous 40% sodium hydroxide solution, then washed at 95°C. with 70 g of water. After decantation and drying in a vacuum, apolyhydroxylated amine having the following formula is obtained:##STR52## wherein R represents a hydrocarbon radical derived fromisostearic acid, and n has a statistical average value of 1.

The compound is a straw-yellow oil.

Examples 19-28 which illustrate the preparation of additional surfaceactive agents in accordance with this embodiment of the presentinvention are set forth below in Table I.

                                      TABLE I                                     __________________________________________________________________________    Step (a)                                                                                                                       Hydroxyl Index Of                                    Catalyst  Glycerol       Resulting                                                                     Polyhalogenated              Example                                                                            Alcohol            BF.sub.3 /CH.sub.3 COOH                                                                 Epichlorohydrin                                                                              Polyether                    No.  R       (Grams)                                                                             Moles                                                                              (ml)      (Grams)                                                                             Moles                                                                              n + 1                                                                             Found  Theoretical           __________________________________________________________________________    19   cetyl/stearyl                                                                         143   0.5  1.5       462.5 5    10  57-58  46                    20   "       532   2.1  2.2       370   4    1.9 128    131                   21   "       "     "    "         "     "    "   "      "                     22   "       "     "    "         "     "    "   "      "                     23   *residue of                                                                           410   2    3         832   9    4.5 95.5   90.5                       Dobanol                                                                  24   Hexadecyl                                                                             132   0.5  0.8       185   2    4   95     88                    25   Nonylphenyl                                                                           220   1    1         185   "    2   145    138                   26   "       114.5 0.5  0.7       "     "    4   108                          27   "       "     "    "         "     "    "   "                            28   "       220   1    1         185   2    2   145    138                   __________________________________________________________________________    Step (b)              Step (c)                 Step (d)                            Polyhalogenated Poly-                                                                    NaOH                      Reaction       Potassium            Example                                                                            ether (from Step a)                                                                      (40% soln.)                                                                         Secondary Amine     Time Solvent   Acetate              No.  (Grams)                                                                             Moles                                                                              (Grams)                                                                             Name      (Grams)                                                                            % Excess                                                                           (Hours)                                                                            Type (Grams)                                                                            (Grams)              __________________________________________________________________________    19   200   0.2**                                                                              22.8  Piperidine                                                                              23   5    1.5  DPG  400  148.5                20   214.5 0.49 54    Morpholine                                                                              44.7 5    "    DEG  300  --                   21   200   0.45 50    Diethanolamine                                                                          50.8 5    "    "    "    --                   22   "     "    "     Diisopropanolamine                                                                      65.5 5    "    "    320  --                   23   1200  2.09 219   Diethanolamine                                                                          244  10   2    "    1200 720                  24   190   0.3  50    Morpholine                                                                              27.5 5    2    BDG  206  93                   25   202   0.5  55    Diethanolamine                                                                          57.5 5    2.5  DEG  300  --                   26   125   0.24 25.4    "       28.2 10   1.5  "    "    --                   27   "     "    "     Morpholine***                                                                           23.2 10   3    "    180  --                   28   150   0.33 36.3  Morpholine****                                                                          30.2 5    1.5  "    150  --                   __________________________________________________________________________    Step (d)                                   Analysis                                                Alcoholysis                                                                            Saponifi-   Index Of Hydroxy-                                                                       Solubility                                Time Absolute cation      lated Amine of                                                                          Index Of                             NaOH At   Ethyl    NaOH-40%                                                                            Salting                                                                             The Invention                                                                           Saponifi-                                                                           In                  Example                                                                            CH.sub.3 COOH                                                                       40%  185° C.                                                                     Alcohol  Soln. Out   Found                                                                              Theoret-                                                                           cation                                                                              acidified           No.  (Grams)                                                                             (Grams)                                                                            (Hours)                                                                            + trace MeONa                                                                          (Grams)                                                                             (in water)                                                                          (meq/g)                                                                            ical Found.sup.#                                                                         Water               __________________________________________________________________________    19   --    --   6    +        --    --                    +                   20   26    43.5 3    --       --    +     2    2.06 0.25  +                   21   24.6  41   4.5  --       --    with BDG                                                                            1.8  2    0.14  +                   22   24.6  41   3    --       --    +     1.85 1.89 0.17  +                   23   --    --   6    --       --    --              0.39  +                   24   --    --   5    --       72    +     1.65 1.60 0     +                   25   30    47   5    --       +     --    1.9  1.80 0.38  (Cloudy)            26   36.8  61.2 3.25 --       --    --    1.97 1.89 0.5   +                   27   36.8  61   3    --       --    --    1.96 2    0.23  +                   28   23.8  40   3    --       --    --    1.9-2                                                                              1.8  0.38  +                   __________________________________________________________________________     *Dobanol (Shell) Mixture of saturated principally straight chained            aliphatic alcohols having 11-15 carbon atoms (14% branched chained).          **200 g dipropylene glycol added as solvent                                   ***180 g dipropylene glycol added as solvent                                  ****150 g tertiobutyl alcohol added as solvent                                .sup.# Theoretical Index Of Saponification = 0                                DEG = Diethylene glycol                                                       BDG = butyl diglycol                                                          DPG = Dipropylene glycol                                                      MeONa = sodium methylate                                                 

III. Surface Active Agents Which Are The Condensation Product Of AnAlcohol, An Epoxide And Glycerol Epihalohydrin

In accordance with this embodiment of the present invention there areprovided cationic surface-active agents selected from the groupconsisting of:

(1) agents having the formula ##STR53## which are hydroxylatedcondensation products of an alcohol having the formula R'OH, an epoxidehaving the formula ##STR54## and glycerol epihalohydrin, wherein R' is ahydrophilic group selected from the class consisting of linear orbranched alkyl and alkenyl having 12-20 carbon atoms, R" represents amember selected from the group consisting of methyl and ethyl, m has astatistical average value of 2-6, R₁ and R₂ each independently areselected from the group consisting of lower alkyl having 1-4 carbonatoms, lower hydroxyalkyl having 1-4 carbon atoms or together with thenitrogen atom to which they are attached form a ring selected from thegroup consisting of morpholine and piperidine and n has a statisticalaverage value of 0.5-4; and

(2) agents which are the quaternary ammonium salts of (1) having theformula ##STR55## wherein R', R", R₁, R₂, m and n have the meaning givenabove, R₃ is selected from the group consisting of methyl and ethyl andY is an anion selected from the group consisting of Cl, Br, I, SO₄ CH₃,SO₄ C₂ H₅, CH₃ SO₃ and ##STR56##

The cationic surface active agents of this embodiment of the presentinvention are prepared by

(a) condensing on a fatty alcohol having the formula R'OH wherein R' hasthe meaning given above, m moles of an epoxide or mixture of epoxideshaving the formula ##STR57## wherein R" has the meaning given above toform a compound having the formula

    R'O[C.sub.2 H.sub.3 (R")O--.sub.m H                        (VIII);

(b) condensing on the compound represented by formula VIII, (n+1) molesof glycerol epihalohydrin having the formula ##STR58## wherein n has themeaning give above and X is halogen, preferably chlorine or bromine toform a mixture of polyhalogenated polyethers having the formula

    R'O--C.sub.2 H.sub.3 (R")O].sub.m [C.sub.2 H.sub.3 (CH.sub.2 X)O--.sub.n CH.sub.2 --CHOH--CH.sub.2 --X                             (IX);

(c) dehydrohalogenating said polyhalogenated polyethers from step (b)with an alkali metal or an alkaline earth metal hydroxide to form amixture of polyhalogenated glycidyl ethers having the formula ##STR59##

(d) reacting the polyhalogenated glycidyl ethers from step (c) with asecondary amine to form a mixture of polyhalogenated tertiary amineshaving the formula ##STR60##

(e) replacing the halogen by hydroxyl in the polyhalogenated tertiaryamines from step (d) to form a mixture of polyhydroxylated tertiaryamines having formula VI given above.

The various steps in the above process for preparing the surface activeagents represented by formula VI are as follows: ##STR61##

The quaternization of the surface-active agents represented by formulaVI yields quaternary ammonium salts having the formula ##STR62## whereinR', R", R₁, R₂, R₃, Y⁻, m and n have the meaning given above.

In the course of the condensation reaction (a) and (b) above, when theepoxy ring is opened during the polycondensation, a mixture of compoundscomprising the structure ##STR63## is obtained.

Thus a mixture of compounds having the general structure --C₂ H₃ (CH₂X)O-- is obtained. Consequently, the hydroxylated compound of formulaeVI and VII given above represents four isomers of each, two of whichresult from the opening of the epoxide ##STR64## the other two resultingfrom the epoxide group of the glycerol epihalohydrin.

In the above formulae m is defined by the equation: ##EQU2## wherein M'is equal to the molecular weight of the alcohol R'OH, E' is equal to themolecular weight of the epoxide ##STR65## and I' is the hydroxyl indexof the condensation product, i.e., the compound represented by formulaVIII above, after step (a).

In the same formulae above, n is defined by the equation: ##EQU3##wherein M is equal to the molecular weight of the alcohol of formulaVIII, E is equal to the molecular weight of the glycerol epihalohydrinand I is the hydroxyl index of the condensation product, i.e., themixture of polyhalogenated polyethers represented by formula IX, afterstep (b).

During the condensation reaction (a) in which m moles of the epoxidehaving formula ##STR66## which epoxide can be for instance propyleneoxide and/or butylene oxide, are reacted on one mole of alcohol havingthe formula R'OH, the number of moles of epoxide fixed by one mole ofalcohol to form the recurring units --C₂ H₃ (R")O] can be greater orsmaller than the value m and a mixture of compounds, all responding togeneral formula VIII are formed, but in which the number of recurringunits varies and all those different numbers are distributedstatistically around a mean value represented by m. Consequently m inthe final product represents the mean value or the average statisticalvalue of the number of recurring units --C₂ H₃ (R")O] fixed on thedifferent compounds having the general formula (VI) or VII.

During the condensation reaction (b) in which (n+1) moles of glycerolepihalohydrin are reacted on one mole of alcohol R'O--C₂ H₃ (R")O]Hdesignated as formula VIII the number of moles of glycerol epihalohydrinfixed by one mole of alcohol VIII to form the recurring units --C₂ H₃(CH₂ OH)O] can be greater or smaller than the value n and a mixture ofcompounds, all responding to general formula IX are formed, but in whichthe number of recurring units --C₂ H₃ (CH₂ OH)O] varies and all thosedifferent numbers are distributed statistically around a mean valuerepresented by n. Consequently n in the final product represents themean value or the average statistical value of the number of recurringunits --C₂ H₃ (CH₂ OH)O] fixed on the different compounds having thegeneral formula VI or VII.

An important fact which should be emphasized and which constitutes oneof the essential advantages of the process of preparing thesurface-active agents of this invention is that the present processresults in the formation of compounds having a single lipophile chainper hydrophile chain.

Moreover, the process of the present invention permits the regulation ofthe hydrophilic and lipophilic properties of the final product. Thehydrophilic characteristic of the resulting surface-active agents can beregulated by choosing the value of the number n of moles of glycerolepihalohydrin reacted with one mole of fatty alcohol. The lipophiliccharacteristics of the resulting surface-active agents can be regulatedby choosing the length of the hydrocarbon chain R in the fatty alcohol.

The following is a detailed description of a preferred embodiment ofproducing the above surface-active agents.

In steps (a) and (b), i.e., the condensation of propylene and/orbutylene oxide on one hand and of glycerol epichlorohydrin orepibromohydrin on the other hand, are carried out, one after the other,in the presence of an acid catalyst such as boron trifluoride, stannicchloride or antimony pentachloride, at a temperature of between 25° and160° C. and preferably between 60° and 120° C. if boron trifluoride isused. The proportion of BF₃ with respect to the total mass of thereactants is between 0.1 and 1% by weight.

In step (c) the polyhalogenated polyethers represented by formula (IX)above, which result from step (b), are converted to glycidyl ethers(formula X) by dehydrohalogenation of the halohydrin, using an aqueoussolution of an alkali or alkaline earth metal hydroxide, having aconcentration, by weight, of from 20 to 50%. The molar ratio of alkalior alkaline earth metal hydroxide to polyhalogenated polyethers rangesbetween 1:1 and 1:2 and preferably from about 1:1.2 to 1:1.5. Duringthis phase of the overall process, which ordinarily is initiallyconducted at about 20° C. or ambient temperature, the reactiontemperature rises to about 100° C. When the exothermicity of thereaction ceases, the reaction is terminated by heating the reactionmixture in a water bath. This dehydrohalogenation operation is generallyconducted in the presence of a solvent to obtain high reaction speedsand high epoxidation yields. The solvent employed should, preferably,not be miscible with concentrated aqueous solutions of electrolytes sothat the resulting polyhalogenated glycidyl ethers can be separated fromthe reaction medium simply by decantation. Tertiary butyl alcohol and2-butoxy ethanol are particularly useful solvents when used in weightproportions essentially equal to that of the halohydrin to bedehydrohalogenated. Quaternary ammonium salts comprising a lipophilechain can be used to improve the contact between the reactants. Theresulting polyhalogenated glycidyl ethers if desired, can be isolated byevaporation of the solvent or it can be used in solution in thesubsequent stage, i.e., step (d).

In a step (d) the polyhalogenated glycidyl ethers from step (c) arereacted with a secondary amine at temperatures of from 25° to 120° C. toopen the epoxide ring and thereby form the polyhalogenated tertiaryamines having formula XI.

Alternatively the polyhalogenated tertiary amines of formula XI can beobtained in a single step by reacting the polyhalogenated polyethersfrom step (b) directly with a secondary amine in the presence of analkali or alkaline earth metal hydroxide.

Representative secondary amines usefully employed in the presentinvention include diethylamine, dipropylamine, morpholine, piperidine,and alkanolamines such as diethanolamine, diisopropanolamine,diglycerylamine and N-ethylethanolamine.

The molar ratio of secondary amine to epoxide (when the glycidyl ethersresponding to formula IX are isolated) and the molar ratio of secondaryamine:halohydrin (when the secondary amine is reacted directly withoutisolating the glycidyl ethers responding to formula IX) are betweenabout 1:1 and 1:1.5, the preferred ratio being about 1:1.5.

In step (e) the replacement of the halogen by a hydroxyl in thepolyhalogenated tertiary amine from step (d), or from its alternateroute, yields the polyhydroxylated amines of the present invention whichare useful surface-active agents and which are represented by formulaVI. This operation is carried out with an alkaline salt of carboxylicacid, such as sodium or potassium acetate, at a temperature of between150° and 200° C., preferably, about 180° C., in the presence or absenceof a solvent.

The presence of a solvent in the reaction medium during step (e) assuresboth instantaneous and progressive contact among the reactants and easyseparation therefrom of the mineral halide formed. Suitable solventsinclude ethylene glycol, diethylene glycol, propylene glycol,dipropylene glycol, as well as the monoalkylethers of these diols, suchas monobutyl ether of ethylene glycol and monobutyl ether of diethyleneglycol. The hydroxylated solvents also intervene by alcoholysis of theesters formed in an intermediate step.

When the reaction is carried out in the absence of a solvent, as may bethe case when the alkaline salt of carboxylic acid is somewhat solublein the reaction medium, the polyhydroxylated tertiary amine is obtainedby alcoholysis of the esters of carboxylic acid with a lower alcoholsuch as methanol or ethanol, or by saponification followed by saltingout or extraction.

In one preferred commercial embodiment, the polyhalogenated polyethersfrom steps (a) and (b) are reacted with a secondary amine, as definedabove in the presence of an alkali or alkaline earth metal hydroxide,without isolating the glycidyl ethers thus formed. After reaction withan alkaline salt of carboxylic acid, the esterified amino ethers areseparated from the mineral halide by filtration or washing, and then thesalts of carboxylic acid are regenerated in situ from the carboxylicesters by saponification with an alkaline hydroxide. Thus, the alkalinesalt of carboxylic acid is recovered in aqueous solution and can be usedfor another hydroxylaton reaction.

As stated above, the surface-active agents of this embodiment of thepresent invention also include the quaternary ammonium salts of thecompounds represented by formula VI, the quaternary ammonium salts beingrepresented by formula VII. To produce said quaternary ammonium salts,the compounds represented by formula VI can be reacted with, forinstance, a quaternizing agent such as methyl sulfate, ethyl sulfate,ethyl chloride, ethyl bromide, methyl iodide, methyl paratoluylenesulfate or methyl methane sulfonate. The mole ratio of quaternizingagent to the compounds represented by formula VI corresponds to thestoichiometric amount or is slightly inferior and the reaction iscarried out at a temperature ranging from 15° to 100° C. at atmosphericpressure.

Compared, for example, with fatty amines, the surface-active agents ofthis embodiment of the present invention lack the odor characteristic offatty amines and their derivatives, have a low melting point, aresaturated and consequently do not become rancid.

Additionally, the process of the present invention yields stablesurface-active agents which are soluble in water without theintroduction of supplementary ionic groups, and especially anionicgroups which impair the substantive characteristics of thesurface-active agents. Further, the surface-active agents of thisinvention are considerably less irritating to the skin and to mucousmembranes than are the fatty amines and their derivatives.

The surface-active agents of the present invention also comparefavorably with amino polyethers having the formula ##STR67## and thesubstitution of a --C₂ H₃ (CH₂ OH)O-- group for the oxyethylene group--OCH₂ CH₂ -- is very useful.

The surface-active agents of this invention, because of their physicaland chemical characteristics, are suitably employed in cosmeticpreparations, shampoos, permanent waving compositions and particularlyin hair dye and hair rinse compositions. Further, when the surfaceactive agents of this embodiment of the present invention, andespecially those represented by formula VI are used in compositions fortreating hair, they impart to the hair a certain sheen and a pleasingtexture. The hair is particularly soft, odorless and is easilyuntangled.

Thus, in accordance with the present invention there is provided ashampoo composition comprising an aqueous solution of the surface activeagents of this invention present in amounts of about 0.5 to 6 percent byweight of said shampoo composition, having a pH ranging from about 3 to6.5. The pH can be adjusted to the desired value by incorporating intosaid composition an acidic component such as lactic, acetic or citricacid and the like.

In another embodiment of the present invention hair is permanently wavedby applying to the hair wound on curlers during the first stage, i.e.,during the reducing stage, a composition comprising reducing agent,permitting the composition to remain on the hair for a time sufficientto alter the disulphide bonds of the keratin of the hair, generallyabout 10-40 minutes, thoroughly rinsing the hair to remove residualreducing agent and applying in the second stage, i.e., during theneutralization stage, a cosmetic composition comprising a mixture of anoxidizing or neutralizing agent and the surface-active agent of thepresent invention, whereby the disulphide bonds of the keratin of thehair are reformed.

Conventional reducing agents employed are advantageously those organicthiols which are generally used to perform the first stage of apermanent waving operation. Representative thiols include thioglycolicacid and its salts, glycol thioglycolate, glycerol thioglycolate,thioglycolic amide, thiolactic acid, glycol thiolactate,β-mercaptoethanol, N-carboxymethyl mercapto acetamid, β-mercaptopropionic acid, and the like. Generally the composition comprising thereducing agent in an aqueous solution of said reducing agent present inamounts of about 2 to 15 percent by weight thereof and having a pHranging from about 8 to 10.

The neutralizing composition of the present invention comprises anaqueous solution of 0.5 to 4 weight percent of a conventionalneutralizing or oxidizing agent and about 0.2 to 15 weight percent of thsurface-active agent of this invention. Conventional neutralizing agentsemployed include, for instance, hydrogen peroxide, sodium or potassiumbromate, sodium perborate or percarbonate and the like.

The surface-active agents of the present invention are also usefullyemployed in hair dye compositions comprising a solution in a solventselected from the group consisting of water and an aqueous solution of alower alkanol such as ethanol and isopropanol of a glycol such as butylglycol, propylene glycol, ethylene glycol, 3-amyloxy 4-propane, 1,2-dioland of a monoalkyl ether of glycol such as monobutyl ether of ethyleneglycol wherein said alkanol and/or glycol and/or ether of glycol ispresent in amounts of about 8 to 25 percent by weight of said solution,a hair dye such as azo, anthraquinone and nitro dyes of the benzeneseries, and 0.5 to 6 percent by weight of the surface-active agent ofthe present invention.

Additionally, if desired, said hair dye composition can include itsweight of hydrogen peroxide to provide said composition in gel form.

Generally the dye is present in amounts of about 0.1 to 5 percent byweight of said composition which has a pH ranging from about 8 to 10.5.

Representative dyes include paraphenylene diamine, 2,5-toluene diaminesulfate, chloroparaphenylene diamine sulfate, nitroparaphenylenediamine, 1,2,4-triaminobenzene trihydrochloride, paraaminodiphenylamino, ortho phenylene diamine, 4-chloro ortho phenylene diamine,4-nitro ortho phenylene diamine, paraaminophenol, 4-amino 2-methylphenol sulfate, 4-amino-3-methyl phenol, 4-amino 2-nitro phenol,m-diamino anisol and its sulfate, p-aminophenol and its sulfate,nitro-p-phenylene diamine, p-toluylene diamine, resorcine, hydroquinone,3-nitro 4-β-aminoethylamine anisole hydrochloride, 2-4-diaminophenolhydrochloride, paramethyl aminophenol sulfate, ortho aminophenol,4-chloro 2-aminophenol, 4-nitro 2-aminophenol, 5-nitro 2-aminophenol,4,6-dinitro 2-aminophenol, 6-chloro 4-nitro 2-aminophenol hydrochloride,4-amino diphenylamine, 4,4'-diamino diphenylamine sulfate, metaphenylenediamine, chloro-meta phenylene diamine, nitro-meta phenylene diamine,meta toluylene diamine, 2,4-diamino anisol sulfate, meta aminophenol,3,5-diaminophenol hydrochloride, diethyl meta aminophenol, paraaminoortho cresol, 1-dimethylamino 3-amino ethylamino 4-nitro benzene,1-hydroxy-2,4-di(p-trimethylammoniumphenylamine) anthraquinonemethosulfate, 1-hydroxy-2,4-di (p-trimethyl-ammoniumphenylamino)anthraquinone iodide, 1-amino propylamino anthraquinone,1,8-Bis-γ-aminopropylamino anthraquinone, 1-diethylamino2-ethylamino-nitro-4-NN-dihydroxyethylamino benzene dihydrochloride,4-N-methylamino-3-nitro-1-N-β-aminoethylamino benzene, [I-hydroxy-4-(γmethylmorpholinium) propylamine anthraquinone]methyl sulfate,2-β-aminoethylamineanthraquinone, 1,5-di-(β-aminopropylamine)anthraquinone, 1-methylamine-4-amino propylamine anthraquinone, 1-aminopropylamine-anthraquinone 1,4-diamine-5-γaminopropylamine-anthraquinone. Additional examples of commerciallyavailable useful dyes include, as monoazo dyes, Cl Acid Blue 92 (13390)and CI Acid Yellow 23 (19140); as diazo dyes, Cl Acid Orange 24 (20170);as triphenylmethane type dyes, Cl Acid Blue 1 (42045), Cl Acid Violet 19(42685), Cl Acid Blue 22 (42755) and Cl Acid Violet 15 (43525); asxanthene dyes, CI Acid Violet 9 (45190); as azine dyes, Cl Acid Black 2(50420), Cl Acid Blue 59 (50315) and Cl Acid Blue 61 (50330); asanthraquinone dyes, Cl Acid Violet 43 (60730), Cl Acid Blue 80 (61585),Cl Acid Violet 51 (62165) and Cl Acid Blue 138 (62075); as premetallizeddyes, both 1:1 and 2:1 complexes, chromium and cobalt, for instance ClDisperse Blue 14 (61500), Cl Disperse Blue 6 (62050) and Cl DisperseBlue 31 (64505); as direct dyes, Cl Direct Blue 2 (22590), Cl DirectBlack 51 (27720) and Cl Direct Violet 51 (27905); and as solvent dyes,(15680) and Cl Solvent Violet 10 (45190).

The surface-active agents of the present invention are also usefullyused in hair rinses. These hair rinses are employed on the hair in orderto make easier its disentanglement, especially when same is electric orcurly. These hair rinses comprise a solution in a solvent selected fromthe group consisting of water and an aqueous solution of a lower alkanolsuch as ethanol and isopropanol wherein said alkanol is present inamounts of about 15 to 60% by weight of said solution, a cosmetic resinin amounts of about 0.5 to 5% and 0.1 to 2% by weight of surface-activeagents of the present invention. This composition may also comprise aperfume in amounts of about 0.05 to 0.5% and hair dyes from an amount ofabout 0.005 to 3% of said composition which has a pH from about 7 to 8.5Representative cosmetic resins include polymers, i.e. polyvinylpyrrolidone (PVP) having a molecular weight ranging between 40,000 to360,000 the preferred molecular weight being 40,000, or copolymers suchas the copolymer of polyvinyl pyrrlidone and vinyl acetate(MW=40,000-160,000) 70%:30% to 30%:70%, the preferred proportion being60%:40% having a viscosity of 3,3 to 4 centipoises in 5% solution inethanol; or copolymers of crotonic acid and vinyl acetate 90%:10% havinga molecular weight of 40,000 to 200,000 and preferably of 50,000 and aviscosity of 7 to 9 centipoises in 5% solution in tetrachlorethane; ormonoalkyl ester of the copolymer of methylvinyl ether and maleic acid.

Representative hair dyes include direct dyes such as azo dyes,triphenylmethane type dyes, xanthene dyes, anthraquinone dyes, azinedyes, premetallized dyes, solvent dyes and the like. All the above citeddyes as commercially available useful dyes may be used.

In use, the compounds of the present invention can be in the form ofsalts of inorganic and organic acids such as hydrochloric, phosphoric,boric, acetic, citric and lactic acids.

IV. Preparation Of Surface-Active Agents Which Are The CondensationProduct Of An Alcohol, An Epoxide And Glycerol Epihalohydrin Example 29

Preparation of a mixture of surface-active agents having the formula##STR68## wherein R' is octadecyl, m has a statistical average value of5.25 and n has a statistical average value of 1.

Steps (a) and (b) Poly addition of propylene oxide and glycerolepichlorohydrin on stearoyl alcohol

6.25 ml of an acetic acid complex of boron fluoride at 36% BF₃ are addedto a molar equivalent quantity of industrial stearoyl alcohol (hydroxylindex: 195 mg KOH/g) dehydrated by heating in a boiling water bath in avacuum and melted.

The mixture is heated to 75°-80° C. Then 5.25 moles of propylene oxideare added drop by drop, the rate of flow being regulated so that thetemperature stays between 75°-80° C. because of the exothermic nature ofthe reaction. When the propylene oxide has been completely used up,which is determined by measurement of the epoxide function in a samplewithdrawn for the purpose, 2 moles of glycerol epichlorohydrin are addeddrop by drop. The temperature is kept constant as before by regulatingthe rate of addition. The polychlorinated polyether having the followingformula is obtained:

    R'O--C.sub.2 H.sub.3 (CH.sub.3)O].sub.m [C.sub.2 H.sub.3 (CH.sub.2 Cl)O].sub.n CH.sub.2 --CHOH--CH.sub.2 Cl,

wherein R', m and n have the meaning given above, the said polyetherhaving a theoretical hydroxyl index of 73.5 (found 90) mg KOH/g.

Steps (c) and (d) dehydrohalogenation and reaction with a secondaryamine

177 g of diisopropanolamine, then 143 g of a 40% sodium hydroxidesolution are added to 776 g of the above polychlorinated polyether.

When the reaction ceases to be exothermic, the mixture is heated to90°-95° C. for 3 hours.

A mixture of polychlorinated tertiary amines having the followingformula is thus obtained: ##STR69## wherein R', m and n have the meaninggiven above.

Step (e) hydroxylation

The excess sodium hydroxide is neutralized with 8 ml of anhydrous aceticacid. 800 ml of butyl monoether of diethylene glycol and 108 g ofpotassium acetate are added. After the water has been removed, themixture is heated to 180°-185° C. for 5 hours.

After cooling to 95° C., 1.8 liters of hot water are added, the mixtureis stirred and decanted and the aqueous phase containing the sodiumchloride which has formed is drawn off.

The water and solvent are evaporated from the organic phase byprogressively raising the temperature to 180° C. under a pressure of 15to 20 mm of mercury.

An oily yellow product is obtained which is soluble in warm water at apH of 3 (the pH being adjusted with lactic acid). Its formula is givenat the top of this example.

This product can also be obtained with the same results by using thesame reactant in the same proportions, but no solvent. In this case, theproduct is de-acetylated by saponification, then separated by saltingout.

Example 30

The procedures of Example 29 are repeated except that comparablyequivalent amounts of butylene oxide are employed in steps (a) and (b)rather than propylene oxide.

Example 31

The procedures of Example 29 are repeated except that comparablyequivalent amounts of glycerol epibromohydrin are employed in steps (a)and (b) rather than glycerol epichlorohydrin.

Examples 32-38

The procedures of Example 29 are repeated except that comparablyequivalent amounts of diethylamine (Ex. 32), morpholine (Ex. 33),piperidine (Ex. 34), diethanolamine (Ex. 35), dipropylamine (Ex. 36),diglycerylamine (Ex. 37) and N-ethylethanolamine (Ex. 38) are employedin step (d) rather than diisopropanolamine.

Example 39

A mixture of surface-active agents having the following formula isprepared: ##STR70## wherein R' is alkyl having 16-18 carbon atoms, m hasa statistical average value of 3 and n has a statistical average valueof 1.

Proceeding as in Example 29, in steps (a) and (b) there are employedrather than stearoyl alcohol and propylene oxide, a mixture of fattyalcohols containing essentially cetyl alcohol and stearyl alcohol havingthe following properties: hydroxyl index, 211; iodine index, 0.5 andfusion point, 52.5° C.; and butylene oxide, respectively, to produce thefollowing polychlorinated polyether,

    R'O--C.sub.2 H.sub.3 (C.sub.2 H.sub.5)O].sub.m [C.sub.2 H.sub.3 (CH.sub.2 Cl)O].sub.n CH.sub.2 --CHOH--CH.sub.2 Cl

wherein R', m and n have the meaing given above.

Then, 36.5 g of morpholine and 44 g of a 40% aqueous solution of sodiumhydroxide are added to 222 g of the above polychlorinated polyether. Theaddition of the sodium hydroxide takes 15 minutes and the resultingmixture is then heated in a water bath for three hours. Apolychlorinated tertiary amine having the following formula is thusobtained, ##STR71##

The excess sodium hydroxide is neutralized with 2.4 g of glacial aceticacid and the reaction mixture is diluted with an equivalent weight ofdipropylene glycol. Then 35 g of anhydrous potassium acetate are addedand the mixture is heated to 180°-185° C. for five hours after the waterhas been removed.

After evaporation of dipropylene glycol under reduced pressure, thede-acetylation is completed by saponification using 5 g of an aqueous40% solution of sodium hydroxide. It is then washed twice with 250 ml ofboiling water and the organic phase is then dehydrated by being heatedin a vacuum. 211 g of a red-brown oil, having the formula given at thebeginning of the example, are collected.

Example 40

Preparation of a mixture of surface-active agents having the formula##STR72## wherein R' is dodecyl, m has a statistical average value of 2and n has a statistical average value of 4.

Steps (a) and (b) Polyaddition of propylene oxide and glycerolepichlorohydrin on dodecyl alcohol

0.8 ml of an acetic acid complex of boron fluoride at 36% BF₃ is addedto 0.2 mole (37.2 g) of industrial dodecyl alcohol.

The mixture is heated to 75°-80° C. Then 0.4 mole of propylene oxide isadded drop by drop, the rate of flow being regulated so that thetemperature stays between 75°-80° C. because of the exothermic nature ofthe reaction. When the propylene oxide has been completely used up,which is determined by measurement of the epoxide function in a samplewithdrawn for the purpose, 1 mole (92.5 g) of glycerol epichlorohydrinis added drop by drop. The temperature is kept constant as before byregulating the rate of addition. The polychlorinated polyether havingthe following formula is obtained:

    R'O--C.sub.2 H.sub.3 (CH.sub.3)O].sub.m [C.sub.2 H.sub.3 (CH.sub.2 Cl)O].sub.n CH.sub.2 --CHOH--CH.sub.2 Cl,

wherein R', m and n have the meaning given above, the said polyetherhaving a theoretical hydroxyl index of 73 mg KOH/g.

Steps (c) and (d) dehydrohalogenation and reaction with a secondaryamine

22.5 g of diethanolamine, then 22 g of a 40% sodium hydroxide solutionare added to 0.2 mole (103 g) of the above polychlorinated polyether.

When the reaction ceases to be exothermic, the mixture is heated to90°-95° C. for 2 hours.

A mixture of polychlorinated tertiary amines having the followingformula is thus obtained: ##STR73## wherein R', m and n have the meaninggiven above.

Step (e) hydroxylation

110 g of dipropylene glycol and 44 g of potassium acetate are added.After the water has been removed, the mixture is heated to 180°-185° C.for 4 hours.

The potassium chloride which has formed is eliminated by filtration andthe dipropylene glycol is evaporated under vacuum.

In order to complete the de-acetylation the crude product is dissolvedin 125 ml of absolute ethyl alcohol to which 1 ml of a 25% solution ofsodium methylate in methanol has been added.

After one night at room temperature the product is filtrated. Alcoholand the ethyl acetate which has formed are drawn off.

A brown viscous oily product is obtained which is soluble in water andthe formula of which is represented above.

Example 40 A

The procedures of Example 40 are repeated except that comparablyequivalent amounts of butylene oxide are employed in steps (a) and (b)rather than propelene oxide.

Example 40 B

The procedures of Example 40 are repeated except that comparablyequivalent amounts of glycerol epibromohydrin are employed in steps (a)and (b) rather than glycerol epichlorohydrin.

Examples 40 C-40 J

The procedures of Example 40 are repeated except that comparablyequivalent amounts of diethylamine (Ex. 40 C), morpholine (Ex. 40-D),piperidine (Ex. 40 E), diisopropanolamine (Ex. 40 F), dipropylamine (Ex.40 G), diglycerylamine (Ex. 40 H) and N-ethylethanolamine (Ex. 40 J) areemployed in step (d) rather than diisopropanolamine.

V. Cosmetic Compositions Utilizing As A Component Thereof Surface-ActiveAgents Of The Present Invention Example 41

After application of a conventional permanent-waving compositionconsisting of an aqueous solution of 8% ammonium thioglycolate having apH of 9.5, the hair is rinsed and 100 cm³ of the following solution isapplied in the usual manner:

    __________________________________________________________________________     ##STR74##                           2  g                                     Phosphoric acid                      1.2                                                                              g                                     Hydrogen peroxide, q.s.p.            7  volumes                               Water, q.s.p.                        100                                                                              cm.sup.3                              __________________________________________________________________________

It is noted that the application is simple, the lather goes on easily,it holds well on the curlers, rinses easily and after unrolling, thehair is particularly soft, shiny and odorless and untangles easily.

Example 42

After reduction of the hair with an aqueous solution of the samecomposition as that above, the hair is rinsed and a solution having thefollowing formula is applied as a fixative:

    __________________________________________________________________________     ##STR75##                       1.2 g                                        wherein R = C.sub.12 -C.sub.14 and n has a statistical average value of       0.5.                                                                          Phosphoric acid, q.s.p.          pH = 3.5                                     Hydrogen peroxide, q.s.p.        6 volumes                                    Water, q.s.p.                    100 cm.sup.3                                 __________________________________________________________________________

It will be noted that, as above, the hair is soft, shiny and odorless,and that it combs out and untangles easily.

Example 43

After reduction of the hair with a permanent waving composition havingthe following composition:

    ______________________________________                                        Thioglycolic acid       10 g                                                  Ammonium sesquicarbonate                                                                              10 g                                                  Ammonia, q.s.p.         pH = 8.5                                              Water, q.s.p.           100 cm.sup.3                                          ______________________________________                                    

The hair is left for a while, and then rinsed.

A fixative having the following composition is then applied:

    __________________________________________________________________________     ##STR76##                       3 g                                          wherein R = C.sub.12 -C.sub.14 and n has a statistical average value of       Phosphoric acid                  1.5 g                                        Hydrogen peroxide, q.s.p.        6 volumes                                    Water, q.s.p.                    100 cm.sup.3                                 __________________________________________________________________________

After letting the setting agent act for a certain time, and rinsing, thehair is in very good shape, it untangles easily, is soft, and there isno foam left in it. These improvements in rinsing are due to thepresence in the mixtures of the compounds that is the object of thepresent invention and to the fact that this mixture of compounds ishighly hydrophilic due to the increase in the value of n from 0.5 to 1.

Example 44

After using the same permanent waving composition as before, thefollowing solution is applied as a fixative:

    __________________________________________________________________________     ##STR77##                               1.5 g                                wherein R is a straight chain alkyl having 12 to 14 carbon atoms and n        has a statistical                                                             average value of 0.5.                                                         Citric acid                              0.1 g                                Hydrogen peroxide, q.s.p.                5 volumes                            Water, q.s.p.                            100 cm.sup.3                         __________________________________________________________________________

The results are excellent. Rinsing is facilitated and softness of thehair is particularly pleasing. This is due to the fact that a quaternaryderivative has been used instead of a tertiary as before, and this typeof derivative has a carrier affinity for hair and makes it softer andshinier.

Example 45

A solution having the following composition is prepared:

    __________________________________________________________________________    RO[C.sub.2 H.sub.3 O(CH.sub.2 OH)].sub.nH                                                                      25 g                                         (R = 9-octadecenyl n has a statistical average value of 2)                    RO[C.sub.2 H.sub.3 O(CH.sub.2 OH)].sub.nH                                                                      15 g                                         (R = 9-octadecenyl n has a statistical average value of 4)                    Oleic acid                       3 g                                           ##STR78##                       3 g                                          (R = octadecenyl n has a statistical value of 1)                                                               3 g                                          Butylcellosolve                  8 g                                          Ethanol                          5 g                                          Propylene glycol                 5 g                                          Trilon B (sodium salt of ethylenediamine                                                                       0.3 g                                        tetracetic acid)                                                              Paratolylenediamine              1 g                                          Meta diamino anisol sulfate      0.05 g                                       Meta aminophenol                 0.15 g                                       Para aminophenol                 0.1 g                                        20% ammonia                      13 g                                         Water, q.s.p.                    100 cm.sup.3                                 __________________________________________________________________________

To obtain the gel necessary for dyeing hair it is mixed with equal partsof hydrogen peroxide at 20 volumes. This gel is applied to the hair,left for 30 minutes, rinsed and washed.

A chestnut shade is obtained.

Example 46

A solution having the following composition is prepared:

    __________________________________________________________________________    Nonylphenol oxyethylenated with 4 moles                                                                        25 g                                         ethylene oxide                                                                Nonylphenol oxyethylenated with 9 moles                                                                        15 g                                         ethylene oxide                                                                Oleic acid                       3 g                                           ##STR79##                       3 g                                          wherein R is 9-octadecenyl and n has a statistical average                    value of 1.                                                                   Butyl cellosolve                 10 g                                         Ethanol                          8 g                                          Trilon B (sodium salt of ethylenediamine                                                                       0.3 g                                        tetracetic acid)                                                              Paratolylene diamine             1 g                                          Meta diamino anisol sulfate      0.05 g                                       Meta aminophenol                 0.15 g                                       Para aminophenol                 0.1 g                                        20% concentration ammonia        13 g                                         Water, q.s.p.                    100 cm.sup.3                                 __________________________________________________________________________

To obtain a gel, the above mixture is further admixed with equal partsof hydrogen peroxide at 20 volumes. The resulting gel is applied to thehair, left for 30 minutes, rinsed and washed. A chestnut shade isobtained.

Example 47

A solution having the following composition is prepared:

    __________________________________________________________________________    4-amino-3-nitro-1-Ndiethylaminoethyl) amino benzene                                                            0.5 g                                         ##STR80##                       1 g                                          wherein R = 9-octadecenyl and n has a statistical average                     value of 3                                                                    Water, q.s.p.                    100 cm.sup.3                                 __________________________________________________________________________

The chestnut or light chestnut colored hair is treated directly withthis solution by applying the same thereto and permitting it to remainin contact with the hair for 30 minutes. Thereafter the hair is rinsedand washed and there is imparted thereto a violet mahogany shade.

Example 48

An aqueous solution having the following composition is prepared:

    __________________________________________________________________________     ##STR81##                          10 g                                      (n has a statistical average value of 1)                                      Lactic acid, q.s.p.                 pH = 4                                    Water, q.s.p.                       100 cm.sup.3                              __________________________________________________________________________

10 cm³ of this solution are applied to previously dampened hair and thehair is vigorously rubbed to emulsify all the dirt. The hair is rinsedthoroughly with water, then another 8 to 10 cm³ of the product areapplied. An abundant lather is obtained and the hair is rinsed. The hairthus washed is shiny, soft and is non-electric.

Example 49

An aqueous solution having the following composition is prepared:

    __________________________________________________________________________     ##STR82##                          3.5 g                                     (n has a statistical average value of 1)                                      C.sub.12 H.sub.25 O[C.sub.2 H.sub.3 O(CH.sub.2 OH)].sub.nH                                                        9 g                                       (n has a statistical average value of 4)                                      Lactic acid, q.s.p.                 pH = 3                                    Water, q.s.p.                       100 cm.sup.3                              __________________________________________________________________________

10 cm³ of this solution are applied to previously dampened hair and itis rubbed vigorously to emulsify all the dirt. It is thoroughly rinsedwith water. Then another 8 to 10 cm³ of the above solution are applied.An abundant lather is obtained and the hair is rinsed. Hair thus washedis shiny, soft and non-electric.

Example 50

An aqueous solution having the following composition is prepared:

    __________________________________________________________________________     ##STR83##                          3.5 g                                     (n has a statistical average value of 1)                                      Lauryl alcohol oxyethylenated with 12 moles                                                                       10 g                                      ethylene oxide                                                                Lactic acid, q.s.p.                 pH = 4                                    Water, q.s.p.                       100 cm.sup.3                              __________________________________________________________________________

10 cm³ of this solution are applied to previously dampened hair and itis rubbed vigorously to emulsify all the dirt. It is thoroughly rinsedwith water. Then another 8 to 10 cm³ of the above solution are applied.An abundant lather is obtained and the hair is rinsed. Hair thus washedis shiny, soft and non-electric.

Example 51

An aqueous solution having the following composition is prepared:

    __________________________________________________________________________     ##STR84##                                                                    (R = a C.sub.12 -C.sub.14 alkyl having a linear chain; n has a                statistical                      9 g                                          average value of 0.5)                                                         Lactic acid, q.s.p.              pH = 4                                       Water, q.s.p.                    100 cm.sup.3                                 __________________________________________________________________________

10 cm³ of this solution are applied to previously dampened hair and itis rubbed vigorously to emulsify all the dirt. It is thoroughly rinsedwith water. Then another 8 to 10 cm³ of the above solution are applied.An abundant lather is obtained and the hair is rinsed. Hair thus washedis shiny, soft and non-electric.

Example 52

An aqueous solution having the following composition is prepared:

    __________________________________________________________________________     ##STR85##                       3 g                                          (R = a C.sub.12 -C.sub.14 alkyl having a linear chain; n has a                statistical                      9 g                                          average value of 0.5)                                                         C.sub.12 H.sub.25 O[C.sub.2 H.sub.3 O(CH.sub.2 OH)].sub.nH                                                     9 g                                          (n has a statistical average value of 4)                                      Lactic acid, q.s.p.              pH = 3                                       Water, q.s.p.                    100 cm.sup.3                                 __________________________________________________________________________

10 cm³ of this solution are applied to previously dampened hair and itis rubbed vigorously to emulsify all the dirt. It is thoroughly rinsedwith water. Then another 8 to 10 cm³ of the avove solution are applied.A generous lather is obtained and the hair is rinsed. Hair thus washedis shiny, soft and non-electric.

Example 53

An aqueous solution having the following composition is prepared:

    __________________________________________________________________________     ##STR86##                                                                    (R = a C.sub.12 -C.sub.14 alkyl having a linear chain; n has a                statistical                      3 g                                          average value of 0.5)                                                         Lauryl alcohol oxyethylenated with 12 moles                                                                    12 g                                         ethylene oxide                                                                Lactic acid, q.s.p.              pH = 4                                       Water, q.s.p.                    100 cm.sup.3                                 __________________________________________________________________________

10 cm³ of this solution are applied to previously dampened hair and itis rubbed vigorously to emulsify all the dirt. It is rinsed thoroughlywith water. Then another 8 to 10 cm³ of the above solution are applied.A generous lather is obtained and the hair is rinsed. Hair thus washedis shiny, soft and non-electric.

Example 54

An aqueous solution having the following composition is prepared:

    __________________________________________________________________________     ##STR87##                       9 g                                          (R = alkyl C.sub.12 -C.sub.14 ; n has a statistical average value of 1)       Lactic acid, q.s.p.              pH = 4                                       Water, q.s.p.                    100 cm.sup.3                                 __________________________________________________________________________

10 cm³ of this solution are applied to previously dampened hair and itis rubbed vigorously to emulsify all the dirt. It is thoroughly rinsedwith water. Then another 8 to 10 cm³ of the above solution are applied.A generous lather is obtained and the hair is rinsed. Hair thus washedis shiny, soft and non-electric.

Example 55

An aqueous solution having the following composition is prepared:

    __________________________________________________________________________     ##STR88##                       3.5 g                                        (R = alkyl C.sub.12 -C.sub.14 ; n has a statistical average value of 1)       C.sub.12 H.sub.25 O[C.sub.2 H.sub.3 O(CH.sub.2 OH)[.sub.nH                                                     8 g                                          (n has a statistical average value of 4)                                      Lactic acid, q.s.p.              pH= 5                                        Water, q.s.p.                    100 cm.sup.3                                 __________________________________________________________________________

10 cm³ of this solution are applied to previously dampened hair and itis rubbed vigorously to emulsify all the dirt. It is thoroughly rinsedwith water. Then another 8 to 10 cm³ of the above solution are applied.A generous lather is obtained and the hair is rinsed. Hair thus washedis shiny, soft and non-electric.

Example 56

An aqueous solution having the following composition is prepared:

    __________________________________________________________________________     ##STR89##                             9 g                                    (R = alkyl C.sub.12 -C.sub.14 having a linear chain; n has a statistical      value of 0.5)                                                                 Lactic acid, q.s.p.                    pH = 3                                 Water, q.s.p.                          100 cm.sup.3                           __________________________________________________________________________

10 cm³ of this solution is applied to previously dampened hair and it isvigorously rubbed to emulsify all the dirt. It is thoroughly rinsed withwater. Then another 8 to 10 cm³ of the above solution are applied. Agenerous lather is obtained and the hair is rinsed. Hair thus washed isshiny, soft and non-electric.

Example 57

The following composition is prepared:

    __________________________________________________________________________    Nonylphenol oxyethylenated with 4 moles of 20  g                              ethylene oxide                                                                Nonylphenol oxyethylenated with 9 moles of 25  g                              ethylene oxide                                                                 ##STR90##                                 2   g                              (R' = octadecyl m has a statistical average value of 5.25                     and n has a statistical average value of 1)                                   Redistilled white olein                    2   g                              Butylene glycol                            3   g                              Propylene glycol                           17  g                              20% ammonia                                13  ml                             Paratolylenediamine base                   1   g                              Hydroquinone                               0.15                                                                              g                              Pentasodium salt of diethylene triamine    1.99                                                                              g                              pentacetic acid                                                               Sodium bisulfite, 35° Be'           1.5 ml                             Metadiaminoanisol sulfate                  0.07                                                                              g                              Resorcinol                                 0.47                                                                              g                              Meta-aminophenol                           0.16                                                                              g                              Para aminophenol base                      0.09                                                                              g                              Nitroparaphenylenediamine                  0.0025                                                                            g                              Water, q.s.p.                              100 ml                             __________________________________________________________________________

This is a clear oil. An equal volume of hydrogen peroxide at 20 volumesis added thereto. The resulting mixture forms a firm gel which isapplied to 100% white hair and permitted to remain thereon for 30minutes thereafter the hair is rinsed, shampooed and dried. This dyecompletely covers the white hair which is as a result of the abovetreatment shiny, flexible, springy, non-electric and easy to manage.

Example 58

The following composition is prepared:

    __________________________________________________________________________    Nonylphenol oxyethylenated with 4 moles of 20  g                              ethylene oxide                                                                Nonylphenol oxyethylenated with 9 moles of 25  g                              ethylene oxide                                                                 ##STR91##                                 2   g                              (R' = octadecyl, m has a statistical average value of 5.25                    and n has a statistical average value of 1)                                   Butylene glycol                            3   g                              Propylene glycol                           17  g                              20% ammonia                                13  ml                             Paratolylenediamine base                   1   g                              Hydroquinone                               0.15                                                                              g                              Pentasodium salt of diethylene triamine    1.99                                                                              g                              pentacetic acid                                                               Sodium bisulfite, 35° Be'           1.5 ml                             Metadiaminoanisol sulfate                  0.07                                                                              g                              Resorcinol                                 0.47                                                                              g                              Meta-aminophenol                           0.16                                                                              g                              Para-aminophenol base                      0.09                                                                              g                              Nitroparaphenylenediamine                  0.0025                                                                            g                              Water, q.s.p.                              100 ml                             __________________________________________________________________________

This is a clear oil. An equal volume of hydrogen peroxide at 20 volumesis added thereto. The resulting mixture forms a firm gel which isapplied to 100% white hair and is permitted to remain in contacttherewith for 30 minutes. Thereafter the hair is rinsed, shampooed anddried. This dye completely covers the white hair which is as a result ofthis treatment flexible, springy, non-electric and easy to manage.

Example 59

The following composition is prepared, which forms a clear oil:

    __________________________________________________________________________    RO[C.sub.2 H.sub.3 O(CH.sub.2 OH)].sub.nH   20  g                             (R = 9-octadecenyl and n has a statistical average value of 2)                RO[C.sub.2 H.sub.3 O(CH.sub.2 OH)].sub.nH   20  g                             (R = 9-octadecenyl and n has a statistical value of 4)                         ##STR92##                                  2   g                             (R' = octadecyl, m has a statistical average value of 5.25                    and n has a statistical average value of 1)                                   Redistilled white olein                     2   g                             Butylene glycol                             8   g                             Propylene glycol                            12  g                             20% ammonia                                 13  ml                            Paratolylenediamine base                    1   g                             Hydroquinone                                0.15                                                                              g                             Pentasodium salt of diethylene triamine penta-                                                                            1.99                                                                              g                             cetic acid                                                                    Sodium bisulfite, 35° Be'            1.5 g                             Metadiaminoanisol sulfate                   0.07                                                                              g                             Resorcinol                                  0.47                                                                              g                             Meta-aminophenol                            0.16                                                                              g                             Para-aminophenol                            0.09                                                                              g                             Nitroparaphenylenediamine                   0.0025                                                                            g                             Water, q.s.p.                               100 ml                            __________________________________________________________________________

An equal volume of hydrogen peroxide at 20 volumes is added to the aboveand the resulting mixture forms a firm gel which is applied to 100%white hair. This mixture is left on the hair for 30 minutes. Thereafterthe hair is rinsed, shampooed and dried. The white hair is completelycovered and is shiny, flexible, springy, non-electric and easy tomanage.

Example 60

The following composition is prepared, which forms a clear oil:

    __________________________________________________________________________    RO[C.sub.2 H.sub.3 O(CH.sub.2 OH)].sub.nH   20  g                             (R = 9-octadecenyl; n has a statistical average value of 2)                   RO[C.sub.2 H.sub.3 O(CH.sub.2 OH)].sub.nH   20  g                             (R = 9-octadecenyl; n has a statistical value of 4)                            ##STR93##                                  2   g                             (R' = octadecyl, m has a statistical average value of 5.25                    and n has a statistical average value of 1)                                   Butylene glycol                             8   g                             Propylene glycol                            12  g                             20% ammonia                                 13  ml                            Paratolylenediamine base                    1   g                             Hydroquinone                                0.15                                                                              g                             Pentasodium salt of diethylene triamine penta-                                                                            1.99                                                                              g                             cetic acid                                                                    Sodium bisulfite, 35° Be'            1.5 g                             Metadiaminoanisol sulfate                   0.07                                                                              g                             Resorcinol                                  0.47                                                                              g                             Meta-aminophenol                            0.16                                                                              g                             Para-aminophenol                            0.09                                                                              g                             Nitroparaphenylenediamine                   0.0025                                                                            g                             Water, q.s.p.                               100 ml                            __________________________________________________________________________

An equal volume of hydrogen peroxide at 20 volumes is added to the aboveand the resulting mixture forms a firm gel which is applied to 100%white hair. This mixture is left on the hair for 30 minutes. Thereafterthe hair is rinsed, shampooed and dried. The white hair is completelycovered and is flexible, shiny, springy, non-electric and easy tomanage.

Example 61

A shampoo having the following composition is prepared:

    ______________________________________                                         ##STR94##                    6 g                                             R = a C.sub.12 -C.sub.14 alkyl having a linear chain;                         n has a statistical average value of 1.                                       C.sub.12 H.sub.25O[C.sub.2 H.sub.3 O(CH.sub.2 OH)].sub.4H                                                   12 g                                            Lactic acid q.s.p.            pH 3                                            Water q.s.p.                  100 g                                           ______________________________________                                    

10 cm³ of this solution are applied to previously dampened hair and itis rubbed vigorously to emulsify all the dirt. It is rinsed thoroughlywith water. Then another 8 to 10 cm³ of the above solution are applied.A generous lather is obtained and the hair is rinsed. Hair thus washedis shiny, soft and non-electric.

Example 62

A shampoo having the following composition is prepared:

    ______________________________________                                         ##STR95##                    4 g                                             R = a C.sub.12 -C.sub.14 alkyl having a linear chain;                         n has a statistical average value of 1.                                       Lauryl alcohol oxyethylenated with 12 moles of                                                              15 g                                            ethylene oxide                                                                Lactic acid q.s.p.            pH 5                                            Water q.s.p.                  100 g                                           ______________________________________                                    

This shampoo is used and gives the same results as shampoo of example61.

Example 63

A shampoo having the following composition is prepared:

    ______________________________________                                         ##STR96##                    5 g                                             R = a C.sub.12 -C.sub.14 alkyl having a linear chain;                         n has a statistical average value of 1.                                       Lauryl alcohol oxyethylenated with 12 moles of                                                              10 g                                            ethylene oxide                                                                Lauryl diethanolamide         4 g                                             Lactic acid q.s.p.            pH 5                                            Water q.s.p.                  100 g                                           ______________________________________                                    

This shampoo is used and gives the same results as shampoo of example61.

Example 64

The following composition is prepared:

    __________________________________________________________________________    Nonyl-phenyl oxyethylenated with 4 moles of                                                                        26 g                                     ethylene oxide                                                                Nonyl-phenyl oxyethylenated with 9 moles of                                                                        22 g                                     ethylene oxide                                                                 ##STR97##                           3  g                                     96° Ethyl alcohol             8  g                                     Propyleneglycol                      12 g                                     Ammonia 22° Baume             12 ml                                    Dyes:                                                                         Meta-diaminoanisol sulfate           0.030                                                                            g                                     Resorcine                            0.400                                                                            g                                     Meta-aminophenol base                0.150                                                                            g                                     Para-aminophenol base                0.087                                                                            g                                     Nitro-para-phenylene-diamine         0.004                                                                            g                                     Para-toluylene-daimine               1.000                                                                            g                                     Sodium salt of ethylene diamine tetracetic acid                                                                    3  g                                     Sodium bisulfite d = 1.32            1.200                                                                            g                                     Water q.s.p.                         100                                                                              g                                     __________________________________________________________________________

This compound is mixed with its own volume of hydrogen peroxide at 20volumes. The resulting gel when applied to hair with a paint-brush for30 minutes gives after rinsing and drying a brown shade with a chestnutglint. The hair after treatment is very soft, silky and easy to manage.

Examples 65-66

The same composition is prepared as in example 64 except that

    __________________________________________________________________________     ##STR98##                            3 g                                     is replaced:                                                                  for Example 65                                                                 ##STR99##                            3.5                                                                             g                                     R = 9-octadecenyl                                                             and for Example 66                                                             ##STR100##                           2.5                                                                             g                                     __________________________________________________________________________

These compositions give both the same results as the composition ofexample 64.

Example 67

The following composition is prepared:

    __________________________________________________________________________    Nonylphenol oxyethylenated with 4 moles of ethylene oxide                                                            24 g                                   Nonylphenol oxyethylenated with 9 moles of ethylene oxide                                                            24 g                                    ##STR101##                            3  g                                   Diethanolamide of copra                5  g                                   96° Ethyl alcohol               8  g                                   Propyleneglycol                        10 g                                   Ammonia 22° Baume               12 ml                                  Dyes                                                                          Para-aminophenol base                  0.080                                                                            g                                   Meta-aminoanisol sulfate               0.025                                                                            g                                   Resorcine                              0.300                                                                            g                                   Meta-aminophenol base                  0.060                                                                            g                                   Nitro-paraphenylenediamine             0.003                                                                            g                                   Hydroquinone                           0.170                                                                            g                                   Sodium salt of ethylene diamine tetracetic acid                                                                      3  g                                   Sodium bisulfite d = 1.32              0.800                                                                            g                                   Para-toluylenediamine                  1.050                                                                            g                                   Water q.s.p.                           100                                                                              g                                   __________________________________________________________________________

This compound is mixed with its own volume of hydrogen peroxide at 20volumes. The resulting gel when applied to hair with a paint-brush for30 minutes gives after rinsing and drying a dark chestnut shade with alight chestnut glint. The hair after treatment is very soft, silky andeasy to manage.

Example 68

The following composition is prepared:

    ______________________________________                                        Nonylphenol oxyethylenated with 4 moles of ethylene                                                        22 g                                             oxide                                                                         Nonylphenol oxyethylenated with 9 moles of ethylene                                                        25 g                                             oxide                                                                         Oleic acid                   4 g                                               ##STR102##                  4 g                                              R represents an alkyl radical having 12 to 18 carbon                          atoms                                                                         Butylglycol                  3 g                                              Propyleneglycol              17 g                                             Ammonia 22° Baume     12 ml                                            Dyes                                                                          Resorcine                    0.040 g                                          Meta-aminophenol base        0.060 g                                          Para aminophenol base        0.280 g                                          Nitro-paraphenylenediamine   0.020 g                                          Para-toluylenediamine        0.120 g                                          Hydroquinone                 0.170 g                                          Sodium salt of ethylene diamine tetracetic acid                                                            3 g                                              Sodium bisulfite d = 1.32    0.800 g                                          Water q.s.p.                 100 g                                            ______________________________________                                    

This compound is mixed with its own volume of hydrogen peroxide at 20volumes. The resulting gel when applied to hair with a paint-brush for30 minutes gives after rinsing and drying a light chestnut shade with agolden fair shade. The hair after treatment is very soft, silky and easyto manage.

Example 69

The same composition is prepared as in example 68 except that

    __________________________________________________________________________     ##STR103##                        4 g                                        R = alkyl having 12 to 18 carbon atoms                                        is replaced by                                                                 ##STR104##                        4 g                                        where R represents an alkyl radical derived from                              isostearic acid.                                                              __________________________________________________________________________

This composition gives the same results as the composition of example68.

Example 70

The following composition is prepared:

    __________________________________________________________________________    Cetyl-stearyl alcohol             20 g                                        Oleyl diethanolamide              4  g                                        Cetyl-stearyl sodium sulfate      5  g                                         ##STR105##                       4  g                                        wherein R = cetyl-stearyl                                                     Ammonia 22° Baume          12 ml                                       Dyes                                                                          Meta diamino-anisol sulfate       0.048                                                                            g                                        Resorcine                         0.420                                                                            g                                        Meta-aminophenol base             0.150                                                                            g                                        Nitro-paraphenylenediamine        0.085                                                                            g                                        Para-tolylenediamine              0.004                                                                            g                                        Sodium salt of ethylene diamine tetracetic acid                                                                 1  g                                        Sodium bisulfite d = 1.32         1.200                                                                            g                                        Water q.s.p.                      100                                                                              g                                        __________________________________________________________________________

30 g of this composition are mixed with 45 g of hydrogen peroxide at 20volumes. A smooth, firm cream is obtained which sticks to the hair andis pleasant to use. When applied to 100% gray hair, the result, aftershampooing, is a fair shade. The hair, after treatment is bright, has asilky touch and is easy to manage.

Example 71

The same composition is prepared as in example 70 except that

    __________________________________________________________________________     ##STR106##                         4 g                                       R = cetyl-stearyl                                                             is replaced by:                                                                ##STR107##                         3 g                                       R = cetyl/stearyl                                                             __________________________________________________________________________

This composition gives the same results as the composition of example70.

Example 72

The following composition is prepared:

    __________________________________________________________________________    1,8-Bis-γ-aminopropylamino anthraquinone                                                                 0.15                                                                              g                                        1-diethylamino 2-ethylamino-nitro-                                            4-NNdihydroxyethylamino benzene dihydrochloride                                                                0.6 g                                        4-Nmethylamino-3-nitro-1-Nβ-aminoethylamino benzene                                                       0.25                                                                              g                                        [I-hydroxy-4 (γ methylmorpholinium) propylamino anthra-                                                  0.1 g                                        quinone] methyl sulfate                                                       2-β-aminoethylamino- anthraquinone                                                                        0.2 g                                        1,5-di-(β-aminopropylamino) anthraquinone                                                                 0.3 g                                        1-dimethylamino-3-amino ethylamino-4-nitro benzene                                                             0.3 g                                        1-methylamino-4-amino propylamino anthraquinone                                                                0.3 g                                        1-amino propylamino-anthraquinone                                                                              0.15                                                                              g                                        1,4-diamino-5-γ aminopropylamino-anthraquinone                                                           0.4 g                                        3-nitro-4-β-aminoethylamino-anisole, monohydrochloride                                                    0.2 g                                         ##STR108##                      4   g                                        R = nonylphenyl                                                               diethanolamide of copra          4   g                                        "Trilon X100" (iso octyl phenol with 10 moles of ethylene                                                      10  g                                        oxide                                                                         3-amyloxy-1,2-propane diol       3   g                                        butylglycol                      6   g                                        monoethanolamine q.s.p.          pH 9.5                                       water q.s.p.                     100 g                                        __________________________________________________________________________

This composition is applied as a shampoo for 20 to 30 minutes onchestnut hair with 30 to 70% gray hair. After rinsing a uniform darkchestnut shade is obtained masking the gray hair.

The presence of the compound (I) according to the present applicationimproves the uniformity of the shade on permanent waved hair and permitsa pleasant use.

Example 73

The following hair rinse composition is prepared:

    __________________________________________________________________________    Copolymer of vinyl pyrrolidone and vinyl                                                                      2  g                                          acetate 60:40                                                                 (PVP/VA S 630 of GAF Corp. New-York NY)                                       Ethyl alcohol q.s.p.            20°                                     ##STR109##                     0.5                                                                              g                                          wherein R is an alkyl having 12 to 14 carbon atoms                            Perfume                         0,2                                                                              g                                          Water q.s.p.                    100                                                                              cc                                         __________________________________________________________________________

A direct dye may be added to this composition.

After shampooing, rinsing and wiping, 20 ml of this composition areapplied to the hair which is then permanently waved and dried.

Example 74

    __________________________________________________________________________    Copolymer of vinyl acetate and crotonic acid                                                                 1.5 g                                          (MW 20,000)                                                                   (Resin 28 1310 of National Starch and Chemical                                Corp. New York NY)                                                            Aminomethyl propane diol q.s.p.                                                                              pH 8.5                                         Ethyl alcohol q.s.p.           50°                                      ##STR110##                    0.6 g                                          wherein R represents an alkyl radical                                         having 12 to 14 carbon atoms.                                                 Perfume                        0.2 g                                          Water q.s.p.                   100 cc                                         __________________________________________________________________________

After shampooing, rinsing and wiping, 20 ml of this composition areapplied to the hair which is then permanently waved and dried.

Example 75

    __________________________________________________________________________    Copolymer of vinyl acetate and crotonic acid (MW = 20,000)                                                            1.2                                                                              g                                  (Resin 28 1310 of National Starch and Chemical                                Corp., New-York NY)                                                           Aminoethyl propanol q.s.p.              pH 7                                  Ethyl alcohol q.s.p.                    50°                            Copolymer of vinylpyrrolidone and vinyl acetate                                                                       0.5                                                                              g                                  60:40                                                                         (PVP/VA S 630 of GAF Corp. New-York NY)                                        ##STR111##                             0.4                                   Perfume                                 0,2                                                                              g                                  A direct dye may be added to this composition.                                Water q.s.p.                            100                                                                              cc                                 __________________________________________________________________________

After shampooing, rinsing and wiping, 20 ml of this composition areapplied to the hair which is then permanently waved and dried.

Example 76

    __________________________________________________________________________    Monobutyl ester of the copolymer methyl vinyl                                                                    3  g                                       ether and maleic acid (50% solution)                                          (Resin Gantrez ES 425 of GAF Corp. New-York NY)                               Triethanolamine q.s.p.             pH 7                                       Ethyl alcohol q.s.p.               50°                                  ##STR112##                        0.3                                                                              g                                       wherein R represents a hydrocarbon radical derived                            from isostearic acid                                                          Perfume                            0.3                                                                              g                                       A direct dye may be added to this composition.                                Water q.s.p.                       100                                                                              cc                                      __________________________________________________________________________

After shampooing, rinsing and wiping, 20 ml of this composition areapplied to the hair which is then permanently waved and dried.

What is claimed is:
 1. A cationic surface-active agent having theformula ##STR113## wherein R' is octadecyl, m has a statistical averagevalue of 5.25 and n has a statistical average value of
 1. 2. A cationicsurface-active agent having the formula ##STR114## wherein R' isoctadecyl, R" is ethyl, R₁ and R₂ are each --CH₂ CHOH--CH₃, m has astatistical average value of 2-6 and n has a statistical average valueof 0.5-4.
 3. A cationic surface-active agent having the formula##STR115## wherein R' is octadecyl, R" is methyl, R₁ and R₂ are each--C₂ H₄ OH, m has a statistical average value of 2-6 and n has astatistical average value of 0.5-4.
 4. A cationic surface-active agenthaving the formula ##STR116## wherein R' is octadecyl, R" is methyl, R₁and R₂ are each glyceryl, m has a statistical average value of 2-6 and nhas a statistical average value of 0.5-4.
 5. A cationic surface-activeagent having the formula ##STR117## wherein R' is octadecyl, R" ismethyl, one of R₁ and R₂ is ethyl and the other is --C₂ H₄ OH, m has astatistical average value of 2-6 and n has a statistical average valueof 0.5-4.
 6. A cationic surface-active agent having the formula##STR118## wherein R' is dodecyl, m has a statistical average value of 2and n has a statistical average value of
 4. 7. A cationic surface-activeagent having the formula ##STR119## wherein R' is dodecyl, R" is ethyl,R₁ and R₂ are each --CH₂ --CH₂ OH, m has a statistical average value of2-6 and n has a statistical average value of 0.5-4.
 8. A cationicsurface-active agent having the formula ##STR120## wherein R' isdodecyl, R" is methyl, R₁ and R₂ are each --CH₂ --CHOH--CH₃, m has astatistical average value of 2-6 and n has a statistical average of0.5-4.
 9. A cationic surface-active agent having the formula ##STR121##wherein R' is dodecyl, R" is methyl, R₁ and R₂ are each glyceryl, m hasa statistical average value of 2-6 and n has a statistical average valueof 0.5-4.
 10. A cationic surface-active agent having the formula##STR122## wherein R' is dodecyl, R" is methyl, one of R₁ and R₂ isethyl and the other is --CH₂ --CH₂ OH, m has a statistical average valueof 2-6 and n has a statistical average value of 0.5-4.
 11. A cationicsurface-active agent comprising a mixture of compounds having theformula ##STR123## wherein R' is selected from the group consisting ofalkyl having 12-20 carbon atoms and alkenyl having 12-20 carbon atoms,R" is selected from the group consisting of methyl and ethyl, m has astatistical average value of 2-6, R₁ and R₂ together with the nitrogenatom to which they are attached form a piperidine ring and n has astatistical average value of 0.5-4.
 12. The cationic surface-activeagent of claim 11 wherein R' is dodecyl and R" is methyl.
 13. A cationicsurface-active agent comprising a mixture of compounds having theformula ##STR124## wherein R' is selected from the group consisting ofalkyl having 12-20 carbon atoms and alkenyl having 12-20 carbon atoms,R" is selected from the group consisting of methyl and ethyl, m has astatistical average value of 2-6, R₁ and R₂ each independently areselected from the group consisting of lower alkyl having 1-4 carbonatoms and hydroxy lower alkyl having 1-4 carbon atoms, R₃ is selectedfrom the group consisting of methyl and ethyl, n has a statisticalaverage value of 0.5-4 and Y is an anion selected from the groupconsisting of Cl, Br, I, SO₄ CH₃, SO₄ C₂ H₅, CH₃ SO₄ and ##STR125## 14.A cationic surface-active agent comprising a mixture of compounds havingthe formula ##STR126## wherein R' is selected from the group consistingof alkyl having 12-20 carbon atoms and alkenyl having 12-20 carbonatoms, R" is selected from the group consisting of methyl and ethyl, mhas a statistical average value of 2-6, R₁ and R₂ each independently areselected from the group consisting of lower alkyl having 1-4 carbonatoms and hydroxy lower alkyl having 1-4 carbon atoms or R₁ and R₂together with the nitrogen atom to which they are attached form apiperidine ring, R₃ is selected from the group consisting of methyl andethyl, n has a statistical average value of 0.5-4 and Y is an anionselected from the group consisting of Cl, Br, I, SO₄ CH₃, SO₄ C₂ H₅, CH₃SO₃ and ##STR127##
 15. A cationic surface-active agent comprising amixture of compounds having the formula ##STR128## wherein R' isselected from the group consisting of alkyl having 12-20 carbon atomsand alkenyl having 12-20 carbon atoms, R" is selected from the groupconsisting of methyl and ethyl, m has a statistical average value of2-6, R₁ and R₂ together with the nitrogen atom to which they areattached form a piperidine ring, R₃ is selected from the groupconsisting of methyl and ethyl, n has a statistical average value of0.5-4 and Y is an anion selected from the group consisting of Cl, Br, I,SO₄ CH₃, SO₄ C₂ H₅, CH₃ SO₃ and ##STR129##